Adhesive compositions with polyesters comprising 2,2,4,4-tetraalkyl-1,3-cyclobutanediol and methods of making the same

ABSTRACT

Adhesive compositions comprise a polyester polyol that includes residues of at least one 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diol, including, for example, 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol (TMCD). Adhesive compositions as described herein exhibit enhanced properties as compared to conventional adhesive compositions, and may be suitable for a wide variety of end use applications, including, flexible packaging, woodworking, automotive uses, and electronics.

FIELD OF THE INVENTION

This invention relates to polyurethane adhesives based on polyesterscontaining residues of a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD),and, in particular, residues of 2,2,4,4-tetramethylcyclobutane-1,3-diol(TMCD).

BACKGROUND

Polyurethanes are widely used as adhesives and sealants to bond avariety of substrates. Depending on the applications, polyurethaneadhesives and sealants can be formulated to provide various desirableproperties. However, unmet needs still exist for various applications.For example, improved weatherability can be desirable for outdoorapplications, for example, in building and construction, and in exteriorapplications in automotive and aircraft uses. Thermal stability is oneproperty desirable for auto interior applications. Hydrolytic stabilityand chemical resistance can be desirable for packaging and electronicapplications. Impact resistance can be desirable for auto windshieldmounting. Reduced viscosity can be desirable for ease of applying hotmelt adhesives. Reduced volatile organic compounds (VOC) can beadvantageous for laminating adhesives. Also, a need in the assembly ofparts for consumer electronics is increasingly influenced by theminiaturization of electronic devices where new materials are desirable.In addition, as the global manufacturing industry is transitioning tothe use of more lightweight materials, there is a greater demand fornon-traditional materials. Lightweight materials, such as composites,aluminum and other metal alloys cannot be fastened in the same way astraditional metals. The methods of joining different materials togetheris transitioning from mechanical fasteners like screws, bolts and weldsto adhesives and joints.

Thus, there is a need for polyurethane adhesives/sealants that haveimproved properties for certain end-use applications, such as, forexample, adequate cure time, green bond strength, solvent resistance,chemical resistance, hydrolytic stability, thermal stability, impactresistance, weatherability, improved applicability, and reduced volatileorganic compounds (VOC).

SUMMARY

In one aspect, the present invention concerns a polyester polyolsuitable for use in adhesive compositions, the polyester polyolcomprising: (a) an acid component comprising residues of at least onedicarboxyl monomer; and (b) a diol component comprising residues of (i)a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD); and (ii) at least onediol or polyol other than the TACD, wherein the polyester polyol has ahydroxyl functionality of less than 2.1 and a glass transitiontemperature (Tg) in the range of from about −30° C. to less than 55° C.

In one aspect, the present invention concerns a polyester polyolsuitable for use in adhesive compositions, the polyester polyolcomprising: an acid component comprising residues of at least twodicarboxyl monomers, wherein each of the dicarboxyl monomers are presentin the acid component in an amount of greater than about 5 mole percent,based on the total moles of the acid component; and a diol componentcomprising residues of a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD);wherein the polyester polyol has a hydroxyl functionality of less than2.1 and at least one of the following properties (A) and (B): (A) aglass transition temperature (Tg) in the range of from −30 to 120° C.;and (B) a number average molecular weight (Mn) in the range of from 500to 10,000 g/mole.

In one aspect, the present invention concerns a method of making apolyester polyol suitable for use in an adhesive composition, the methodcomprising reacting at least two dicarboxyl monomers with a2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to form a polyesterpolyol, wherein the polyester polyol has a hydroxyl functionality ofless than 2.1 and at least one of the following properties (A) and (B):(A) a glass transition temperature (Tg) in the range of from −30 to 120°C.; and (B) a number average molecular weight (Mn) in the range of from500 to 10,000 g/mole, wherein the polyester polyol has an acid componentcomprising greater than 5 mole percent of each of residues of each ofthe dicarboxyl monomers, based on the total moles of the acid component.

In one aspect the present invention concerns, an adhesive compositioncomprising (a) a polyester polyol comprising a diol component havingresidues of 2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (b) at leastone isocyanate, wherein the adhesive composition exhibits at least oneof the following properties (i) through (v): (i) an offline bondstrength of 100 to 1000 g/in; (ii) 24-hour bond strength of 200 to 3000g/in; (iii) chemical resistance of 200 to 1000 g/in after boil in bagwith 1:1:1 food simulant; (iv) thermal resistance of 200 to 800 g/in at90° C.; and (v) time to achieve substrate failure of ≤24 hours.

In one aspect, the present invention concerns an adhesive compositioncomprising a prepolymer having an isocyanate functionality comprisingthe reaction product of (i) a polyester polyol comprising the residuesof (A) 2,2,4,4-tetraalkylcyclobutane-1,3-diol in an amount of about 5 toabout 95 mole %, based on the total moles of the diols, (B) at least onediol other than 2,2,4,4-tetraalkylcyclobutane-1,3-diol in an amount ofabout 5 to 95 mole % based on the total moles of the diols, (A) and (B)equaling 100 mole %, and (C) a dicarboxyl compound, and (ii) adifunctional isocyanate, and (b) water or a compound having one or morefunctional groups selected from hydroxyl, amino, ketoacetate, andcarbamate, wherein said adhesive composition exhibits at least one ofthe following properties (i) through (v)-(i) an offline bond strength of100 to 1000 g/in; (ii) 24-hour bond strength of 200 to 3000 g/in; (iii)chemical resistance of 200 to 1000 g/in after boil in bag with 1:1:1food simulant; (iv) thermal resistance of 200 to 800 g/in at 90° C.; and(v) time to achieve substrate failure of ≤24 hours.

In one aspect, the present invention concerns a laminated articlecomprising: a first layer presenting a first surface; a second layerpresenting a second surface; and an adhesive layer disposed between andat least partially in contact with at least one of the first and thesecond surfaces, wherein the adhesive layer is formed from an adhesivecomposition comprising a polyurethane polymer or prepolymer comprising(i) residues of a polyester polyol having a diol component havingresidues of 2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (ii) residuesof at least one isocyanate.

In one aspect, the present invention concerns a method of making anadhesive composition, the method comprising: combining (a) a polyesterpolyol comprising a diol component having residues of2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (b) at least oneisocyanate to form an adhesive composition, wherein the adhesivecomposition exhibits at least one of the following properties (i)through (v): (i) an offline bond strength of 100 to 1000 g/in; (ii)24-hour bond strength of 200 to 3000 g/in; (iii) chemical resistance of200 to 1000 g/in after boil in bag with 1:1:1 food simulant; (iv)thermal resistance of 200 to 800 g/in at 90° C.; and (v) time to achievesubstrate failure of ≤24 hours.

In one aspect, the present invention concerns a method for making alaminated article, the method comprising: providing a first layerpresenting a first surface; applying an adhesive composition to at leasta portion of the first surface; contacting a second surface of a secondlayer with at least a portion of the adhesive composition; and adheringthe first layer to the second layer via an adhesive layer formed by theadhesive composition to form a laminated article, wherein the adhesivelayer comprises a polyester polyol comprising residues of (i) apolyester polyol comprising a diol component having residues of2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (ii) at least oneisocyanate.

In another aspect, the present invention concerns a hot melt adhesivecomposition, the adhesive composition comprising: anisocyanate-terminated polyurethane prepolymer comprising residues of (i)at least one polyester polyol comprising a diol component havingresidues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) atleast one isocyanate, wherein the adhesive composition has a solidscontent of at least 95 percent, based on the total weight of thecomposition.

In one aspect, the present invention concerns a hot melt adhesivecomposition, the adhesive composition comprising: a polyurethaneprepolymer comprising residues of (i) at least one polyester polyolcomprising a diol component having residues of2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least oneisocyanate, wherein at least one property of the adhesive selected fromthe group consisting of green strength, heat resistance, and hydrolyticstability is at least 5 percent higher than the same property exhibitedby an identical adhesive composition formed with a polyurethaneprepolymer having an identical composition as the polyurethaneprepolymer, but having residues of a comparative polyester polyolinstead of said polyester polyol, wherein said comparative polyesterpolyol has an acid component comprising 50 mole % terephthalic acid(TPA) and 50 mole % isophthalic acid (IPA) and a diol componentcomprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethyleneglycol with a hydroxyl number of 45 mg KOH/g, a glass transitiontemperature of 50° C., and a melt viscosity of 130° C. at 60 Pa·s, allother components being the same.

In one aspect, the present invention concerns a method of using anadhesive composition, the method comprising: (a) applying an adhesivecomposition to a first surface of a first substrate to form an adhesivelayer, wherein the adhesive composition comprises a polyurethaneprepolymer having residues of (i) a polyester polyol comprising residuesof 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least oneisocyanate; (b) contacting at least a portion of the adhesive layer witha second surface of a second substrate; and (c) adhering the firstsubstrate and the second substrate to one another via the adhesive layerthereby forming a layered article.

DETAILED DESCRIPTION

The present invention may be understood more readily by reference to thefollowing detailed description of certain embodiments of the inventionand the working examples.

Adhesive compositions described herein may exhibit unique and desirableproperties such as, for example, improved cure time, green bondstrength, solvent resistance, chemical resistance, hydrolytic stability,thermal stability, impact resistance, weatherability, improvedapplicability, and reduced VOC, as compared to conventional adhesivecompositions. Such compositions may include polyester polyols comprisingresidues of at least one 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD),which may itself have unexpected properties capable of impartingenhanced functionality or performance to the adhesive composition. Suchadhesive compositions as described herein may be of several types andmay be suitable for a wide array of end uses, such as, for example,flexible packaging, automotive, building and construction, wood working,assembly of electronic components, and potting for electronics.

Polyester polyols include an acid component and a diol component. Insome embodiments, the diol component may comprise residues of2,2,4,4-tetraalkylcyclobutane-1,3-diol (TACD). TACD is a diol and can berepresented by the general structure:

wherein R₁, R₂, R₃, and R₄ each independently represent an alkylradical, for example, a lower alkyl radical having 1 to 8 carbon atoms,or 1 to 6 carbon atoms, or 1 to 5 carbon atoms, or 1 to 4 carbon atoms,or 1 to 3 carbon atoms, or 1 to 2 carbon atoms, or 1 carbon atom. Thealkyl radicals may be linear, branched, or a combination of linear andbranched alkyl radicals. Examples of TACDs include2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD),2,2,4,4-tetraethylcyclobutane-1,3-diol,2,2,4,4-tetra-n-propylcyclobutane-1,3-diol,2,2,4,4-tetra-n-butylcyclobutane-1,3-diol,2,2,4,4-tetra-n-pentylcyclobutane-1,3-diol,2,2,4,4-tetra-n-hexylcyclobutane-1,3-diol,2,2,4,4-tetra-n-heptylcyclobutane-1,3-diol,2,2,4,4-tetra-n-octylcyclobutane-1,3-diol,2,2-dimethyl-4,4-diethylcyclobutane-1,3-diol,2-ethyl-2,4,4-trimethylcyclobutane-1,3-diol,2,4-dimethyl-2,4-diethyl-cyclobutane-1,3-diol,2,4-dimethyl-2,4-di-n-propylcyclobutane-1,3-diol,2,4-n-dibutyl-2,4-diethylcyclobutane-1,3-diol,2,4-dimethyl-2,4-diisobutylcyclobutane-1,3-diol, and2,4-diethyl-2,4-diisoamylcyclobutane-1,3-diol. In some embodiments, TACDmay comprise or be TMCD.

The TACD residues may be present in the diol component of the polyesterpolyol in an amount of at least 2 mole %, 3 mole %, 5 mole %, 10 mole %,15 mole %, 20 mole %, 25 mole %, 30 mole %, 35 mole %, 40 mole %, 45mole %, 50 mole %, 55 mole %, 60 mole %, 65 mole %, 70 mole %, 75 mole%, 80 mole %, 85 mole %, 90 mole %, or 95 mole % based on the totalresidues of the diol component. Additionally, or in the alternative, thediol component of the polyester polyol may comprise not more than 99mole %, 97 mole %, 95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole%, 70 mole %, 65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40mole %, 35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, or 10mole % of TACD residues, based on the total moles of the diol component.

In one embodiment, the diol component of the polyester polyol maycomprise TACD residues in an amount of about 5 to about 95 mole % or anamount of about 15 to about 60 mole %, based on the total moles of thediols and the polyol equaling 100 mole % (based on the total moles ofthe diol component).

In some embodiments, TACD residues can be present in the diol componentof the polyester polyol in one of the following amounts: 5 to 95 mole %;5 to 90 mole %; 5 to 85 mole %; 5 to 80 mole %; 5 to 75 mole %; 5 to 70mole %; 5 to 65 mole %; 5 to 60 mole %; 5 to 55 mole %; 5 to 50 mole %;5 to 45 mole %; 5 to 40 mole %; 5 to 35 mole %; 5 to 30 mole %; 5 to 25mole %; 5 to 20 mole %; 5 to 15 mole %; 10 to 95 mole %; 10 to 90 mole%; 10 to 85 mole %; 10 to 80 mole %; 10 to 75 mole %; 10 to 70 mole %;10 to 65 mole %; 10 to 60 mole %; 10 to 55 mole %; 10 to 50 mole %; 10to 45 mole %; 10 to 40 mole %; 10 to 35 mole %; 10 to 30 mole %; 10 to25 mole %; 10 to 20 mole %; 15 to 95 mole %; 15 to 90 mole %; 15 to 85mole %; 15 to 80 mole %; 15 to 75 mole %; 15 to 70 mole %; 15 to 65 mole%; 15 to 60 mole %; 15 to 55 mole %; 15 to 50 mole %; 15 to 45 mole %;15 to 40 mole %; 15 to 35 mole %; 15 to 30 mole %; 15 to 25 mole %; 20to 95 mole %; 20 to 90 mole %; 20 to 85 mole %; 20 to 80 mole %; 20 to75 mole %; 20 to 70 mole %; 20 to 65 mole %; 20 to 60 mole %; 20 to 55mole %; 20 to 50 mole %; 20 to 45 mole %; 20 to 40 mole %; 20 to 35 mole%; 20 to 30 mole %, based on the total moles of the diol component.

In some embodiments, TACD residues can be present in the diol componentof the polyester polyol in one of the following amounts: 25 to 95 mole%; 25 to 90 mole %; 25 to 85 mole %; 25 to 80 mole %; 25 to 75 mole %;25 to 70 mole %; 25 to 65 mole %; 25 to 60 mole %; 25 to 55 mole %; 25to 50 mole %; 25 to 45 mole %; 25 to 40 mole %; 25 to 35 mole %; 30 to95 mole %; 30 to 90 mole %; 30 to 85 mole %; 30 to 80 mole %; 30 to 75mole %; 30 to 70 mole %; 30 to 65 mole %; 30 to 60 mole %; 30 to 55 mole%; 30 to 50 mole %; 30 to 45 mole %; 30 to 40 mole %; 35 to 95 mole %;35 to 90 mole %; 35 to 85 mole %; 35 to 80 mole %; 35 to 75 mole %; 35to 70 mole %; 35 to 65 mole %; 35 to 60 mole %; 35 to 55 mole %; 35 to50 mole %; 35 to 45 mole %, based on the total moles of the diolcomponent.

In some embodiments, TACD residues can be present in one of thefollowing amounts: 40 to 95 mole %; 40 to 90 mole %; 40 to 85 mole %; 40to 80 mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65 mole %; 40 to60 mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 95 mole %; 45 to 90mole %; 45 to 85 mole %; 45 to 80 mole %; 45 to 75 mole %; 45 to 70 mole%; 45 to 65 mole %; 45 to 60 mole %; 45 to 55 mole %; 50 to 95 mole %;50 to 90 mole %; 50 to 85 mole %; 50 to 80 mole %; 50 to 75 mole %; 50to 70 mole %; 50 to 65 mole %; 50 to 60 mole %, based on the total molesof the diol component.

In some embodiments, the diol component of the polyester polyol cancomprise residues of at least one diol other than the TACD diol. Suchdiols comprise two hydroxyl groups per molecule, and can be branched orlinear, saturated or unsaturated, aliphatic or cycloaliphatic C₂-C₂₀compounds. The hydroxyl groups on these diols may be primary, secondary,and/or tertiary and, in some embodiments, may be primary diols.

Examples of diols other than TACD suitable for inclusion in thepolyester polyol include 2,2-dimethyl-1,3-propanediol (neopentylglycol), 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol,1,4-benzenedimethanol, ethylene glycol, 1-3-propylene glycol,1-4-propylene glycol, diethylene glycol, dipropylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycol, pentanediol,dodecandiol, and 2,2-bis(hydroxymethyl)propionic acid(dimethylolpropionic acid).

In some embodiments, the diol other than TACD may be selected from2,2-dimethyl-1,3-propanediol (neopentyl glycol),1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol,1,2-propanediol, ethylene glycol, diethylene glycol, and 1,6-hexanediolor mixtures thereof. The diol other than TACD may also be selected fromthe group consisting of diethylene glycol, 1,4-butanediol,1,6-hexanediol, pentanediol, dodecandiol, and combinations thereof.Alternatively, or in addition, the diol other than TACD may be selectedfrom the group consisting of diethylene glycol,1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof.

In some embodiments, the diol component of the polyester polyol cancomprise residues of a diol other than TACD in an amount of at leastabout 3 mole %, at least about 5 mole %, at least about 10 mole %, atleast about 15 mole %, at least about 20 mole %, at least about 25 mole%, at least about 30 mole %, at least about 35 mole %, at least about 40mole %, at least about 45 mole %, at least about 50 mole %, at leastabout 55 mole %, at least about 60 mole %, at least about 65 mole %, atleast about 70 mole %, or at least about 75 mole % and/or not more thanabout 95 mole %, not more than about 90 mole %, not more than about 85mole %, not more than about 80 mole %, not more than about 75 mole %,not more than about 70 mole %, not more than about 65 mole %, not morethan about 60 mole %, not more than about 55 mole %, not more than about50 mole %, not more than about 45 mole %, or not more than about 40 mole%, based on the total moles of the diol component.

In some embodiments, residues of a diol other than TACD can be presentin the diol component of the polyester polyol in one of the followingamounts: 40 to 95 mole %; 40 to 90 mole %; 40 to 85 mole %; 40 to 80mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65 mole %; 40 to 60 mole%; 40 to 55 mole %; 40 to 50 mole %; 45 to 95 mole %; 45 to 90 mole %;45 to 85 mole %; 45 to 80 mole %; 45 to 75 mole %; 45 to 70 mole %; 45to 65 mole %; 45 to 60 mole %; 45 to 55 mole %; 50 to 95 mole %; 50 to90 mole %; 50 to 85 mole %; 50 to 80 mole %; 50 to 75 mole %; 50 to 70mole %; 50 to 65 mole %; 50 to 60 mole %; 55 to 95 mole %; 55 to 90 mole%; 55 to 85 mole %; 55 to 80 mole %; 55 to 75 mole %; 55 to 70 mole %;55 to 65 mole %; 60 to 95 mole %; 60 to 90 mole %; 60 to 85 mole %; 60to 80 mole %; 60 to 75 mole %; 60 to 70 mole %; 65 to 95 mole %; 65 to90 mole %; 65 to 85 mole %; 65 to 80 mole %; 65 to 75 mole %; 70 to 95mole %; 70 to 90 mole %; 70 to 85 mole %; 70 to 80 mole %; 75 to 95 mole%; 75 to 90 mole %; 75 to 85 mole %; 80 to 95 mole %; 80 to 90 mole %,based on the total moles of the diol component.

In some embodiments, the diol component of the polyester polyol maycomprise the following residues: TACD residues in the amount of 15 to 60mole % and the residues of at least one diol other than TACD can bepresent in the amount of 40 to 85%; TACD residues can be present in theamount of 20 to 60 mole % and the residues of at least one diol otherthan TACD can be present in the amount of 40 to 80%; TACD residues canbe present in the amount of 25 to 60 mole % and the residues of at leastone diol other than TACD can be present in the amount of 40 to 75%; TACDresidues can be present in the amount of 30 to 60 mole % and theresidues of at least one diol other than TACD can be present in theamount of 40 to 70%, based on the total moles of the diol component.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (1) TACD residues can bepresent in the amount of 15 to 55 mole % and the residues of at leastone diol other than TACD can be present in the amount of 45 to 85%; or(2) TACD residues can be present in the amount of 20 to 55 mole % andthe residues of at least one diol other than TACD can be present in theamount of 45 to 80%; or (3) TACD residues can be present in the amountof 25 to 55 mole % and the residues of at least one diol other than TACDcan be present in the amount of 45 to 75%; or (4) TACD residues can bepresent in the amount of 30 to 55 mole % and the residues of at leastone diol other than TACD can be present in the amount of 45 to 70%; or(5) TACD residues can be present in the amount of 35 to 55 mole % andthe residues of at least one diol other than TACD can be present in theamount of 45 to 65%; or (6) TACD residues can be present in the amountof 40 to 55 mole % and the residues of at least one diol other than TACDcan be present in the amount of 45 to 60%, based on the total moles ofthe diol component.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (7) TACD residues can bepresent in the amount of 15 to 50 mole % and the residues of at leastone diol other than TACD can be present in the amount of 50 to 85 mole%; or (8) TACD residues can be present in the amount of 20 to 50 mole %and the residues of at least one diol other than TACD can be present inthe amount of 50 to 80 mole %; or (9) TACD residues can be present inthe amount of 25 to 50 mole % and the residues of at least one diolother than TACD can be present in the amount of 50 to 75 mole %; or (10)TACD residues can be present in the amount of 30 to 50 mole % and theresidues of at least one diol other than TACD can be present in theamount of 50 to 70 mole %; or (11) TACD residues can be present in theamount of 35 to 50 mole % and the residues of at least one diol otherthan TACD can be present in the amount of 50 to 65 mole %; or (12) TACDresidues can be present in the amount of 40 to 50 mole % and theresidues of at least one diol other than TACD can be present in theamount of 50 to 60 mole %, based on the total moles of the diolcomponent.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (13) TACD residues can bepresent in the amount of 15 to 45 mole % and the residues of at leastone diol other than TACD can be present in the amount of 55 to 85 mole%; or (14) TACD residues can be present in the amount 20 to 45 mole %and the residues of at least one diol other than TACD can be present inthe amount of 55 to 80 mole %; or (15) TACD residues can be present inthe amount of 25 to 45 mole % and the residues of at least one diolother than TACD can be present in the amount of 55 to 75 mole %; or (16)TACD residues can be present in the amount of 30 to 45 mole % and theresidues of at least one diol other than TACD can be present in theamount of 55 to 70 mole %; or (17) TACD residues can be present in theamount of 35 to 45 mole % and the residues of at least one diol otherthan TACD can be present in the amount of 55 to 65% mole; or (18) TACDresidues can be present in the amount of 40 to 45 mole % and theresidues of at least one diol other than TACD can be present in theamount of 55 to 60 mole %, based on the total moles of the diolcomponent.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (19) TACD residues can bepresent in the amount of 15 to 40 mole % and the residues of at leastone diol other than TACD can be present in the amount of 60 to 85 mole%; or (20) TACD residues can be present in the amount of 20 to 40 mole %and the residues of at least one diol other than TACD can be present inthe amount of 60 to 80 mole %; or (21) TACD residues can be present inthe amount of 25 to 40 mole % and the residues of at least one diolother than TACD can be present in the amount of 60 to 75% mole; or (22)TACD residues can be present in the amount of 30 to 40 mole % and theresidues of at least one diol other than TACD can be present in theamount of 60 to 70 mole %; or (23) TACD residues can be present in theamount of 35 to 40 mole % and the residues of at least one diol otherthan TACD can be present in the amount of 60 to 65 mole %, based on thetotal moles of the diol component.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (24) TACD residues can bepresent in the amount of 15 to 35 mole % and the residues of at leastone diol other than TACD can be present in the amount of 65 to 85 mole%; or (25) TACD residues can be present in the amount of 20 to 35 mole %and the residues of at least one diol other than TACD can be present inthe amount of 65 to 80 mole %; or (26) TACD residues can be present inthe amount of 25 to 35 mole % and the residues of at least one diolother than TACD can be present in the amount of 65 to 75 mole %; or (27)TACD residues can be present in the amount of 30 to 35 mole % and theresidues of at least one diol other than TACD can be present in theamount of 65 to 70 mole %, based on the total moles of the diolcomponent.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (28) TACD residues can bepresent in the amount of 15 to 30 mole % and the residues of at leastone diol other than TACD can be present in the amount of 70 to 85 mole%; or (29) TACD residues can be present in the amount of 20 to 30 mole %and the residues of at least one diol other than TACD can be present inthe amount of 70 to 80 mole %; or (30) TACD residues can be present inthe amount of 25 to 30 mole % and the residues of at least one diolother than TACD can be present in the amount of 70 to 75 mole %, basedon the total moles of the diol component.

In some embodiments, the diol component of the polyester polyol mayinclude one of the following compositions: (31) TACD residues can bepresent in the amount of 15 to 25 mole % and the residues of at leastone diol other than TACD can be present in the amount of 75 to 85 mole%; or (32) TACD residues can be present in the amount of 20 to 25 mole %and the residues of at least one diol other than TACD can be present inthe amount of 75 to 80 mole %, based on the total moles of the diolcomponent.

According to some embodiments, the diol component of the polyesterpolyol may comprise not more than 25 mole % of one or more certain typesof diols. For example, in some embodiments, the diol component of thepolyester polyol may comprise not more than 20 mole %, not more thanabout 15 mole %, not more than about 10 mole %, not more than about 8mole %, not more than about 5 mole %, not more than about 3 mole %, notmore than about 2 mole %, not more than about 1 mole %, or not more thanabout 0.5 mole % of aromatic diols, based on the total moles of the diolcomponent. In some embodiments, the diol component of the polyesterpolyol may comprise not more than 20 mole %, not more than about 15 mole%, not more than about 10 mole %, not more than about 8 mole %, not morethan about 5 mole %, not more than about 3 mole %, not more than about 2mole %, not more than about 1 mole %, or not more than about 0.5 mole %of ethylene glycol, based on the total moles of the diol component.

In some embodiments, the diol component of the polyester polyol mayfurther comprise residues of at least one polyol. As used herein, theterm “polyol” refers to a monomeric compound having at least threehydroxyl groups.

When present, the polyol used to form the polyester polyol describedherein can be branched or linear, saturated or unsaturated, aliphatic orcycloaliphatic C₂-C₂₀ compounds. The hydroxyl groups can be primary,secondary, and/or tertiary, and, in one embodiment, at least two of thehydroxyl groups may be primary. In one embodiment, the polyols may behydrocarbons and may not contain atoms other than hydrogen, carbon andoxygen. Examples of suitable polyols may include, but are not limitedto, 1,1,1-trimethylolpropane (TMP), 1,1,1-trimethylolethane, glycerin,pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol,mixtures thereof, and the like. In one embodiment, the polyol cancomprise TMP.

In some embodiments, the polyester polyol can include a diol componentin which a polyol may be present in an amount of 0 to about 60 mole %,about 0 to about 50 mole %, about 0 to about 40 mole %, about 0 to about30 mole %, about 0 to about 20 mole %, or about 0 to about 15 mole %,based on the total moles of the diol component. In certain embodiments,the polyol may be present in one of the following amounts: 5 to 60 mole%; 5 to 55 mole %; 5 to 50 mole %; 5 to 45 mole %; 5 to 40 mole %; 5 to35 mole %; 5 to 30 mole %; 5 to 25 mole %; 5 to 20 mole %; 5 to 15 mole%; 10 to 60 mole %; 10 to 55 mole %; 10 to 50 mole %; 10 to 45 mole %;10 to 40 mole %; 10 to 35 mole %; 10 to 30 mole %; 10 to 25 mole %; 10to 20 mole %; 15 to 60 mole %; 15 to 55 mole %; 15 to 50 mole %; 15 to45 mole %; 15 to 40 mole %; 15 to 35 mole %; 15 to 30 mole %; 15 to 25mole %; 20 to 60 mole %; 20 to 55 mole %; 20 to 50 mole %; 20 to 45 mole%; 20 to 40 mole %; 20 to 35 mole %; 20 to 30 mole %; 25 to 60 mole %;25 to 55 mole %; 25 to 50 mole %; 25 to 45 mole %; 25 to 40 mole %; 25to 35 mole %; 30 to 60 mole %; 30 to 55 mole %; 30 to 50 mole %; 30 to45 mole %; 30 to 40 mole %; 35 to 60 mole %; 35 to 55 mole %; 35 to 50mole %; 35 to 45 mole; 40 to 60 mole %; 40 to 55 mole %; 40 to 50 mole%; 45 to 60 mole %; 45 to 55 mole %; or 50 to 60 mole %. In oneembodiment, the polyol may be present in the amount of 0 to 60 mole %,while, in another embodiment, the polyester polyol may include a diolcomponent in which the in the amount of 5 to 30 mole %, based on thetotal moles of the diol component.

The polyester polyols described herein also include an acid componentcomprising residues of at least one dicarboxyl monomer. Dicarboxylmonomers may comprises one or more dicarboxylic acids, derivatives ofdicarboxylic acids, or combinations thereof. A dicarboxylic acid mayinclude two carboxylic acid groups, derivatives thereof, or combinationsthereof, capable of forming an ester linkage with a hydroxyl component.Examples of derivatives include, but are not limited to, dimethyl esteror other dialkyl esters of a dicarboxylic acid, a diacid chloride orother diacid halide, or a diacid anhydride. Specific types ofdicarboxylic acids can include, for example, aliphatic dicarboxylicacids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids,derivatives of each, or mixtures of two or more of these acids.

In some embodiments, the acid component of the polyester polyol mayinclude residues of at least two dicarboxyl monomers. In such cases, theresidues of each dicarboxyl monomer may be present in an amount of atleast about 3 mole %, at least about 5 mole %, at least about 10 mole %,at least about 15 mole %, at least about 20 mole %, at least about 25mole %, at least about 30 mole %, at least about 35 mole %, at leastabout 40 mole %, at least about 45 mole %, at least about 50 mole %, atleast about 55 mole %, at least about 60 mole %, at least about 65 mole%, at least about 70 mole %, or at least about 75 mole % and/or not morethan about 95 mole %, not more than about 90 mole %, not more than about85 mole %, not more than about 80 mole %, not more than about 75 mole %,not more than about 70 mole %, not more than about 65 mole %, not morethan about 60 mole %, not more than about 55 mole %, not more than about50 mole %, not more than about 45 mole %, or not more than about 40 mole%, not more than about 35 mole %, not more than about 30 mole %, notmore than about 25 mole %, not more than about 20 mole %, or not morethan about 15 mole %, based on the total moles of the acid component.

In some embodiments, the acid component may consist of, or consistessentially of, residues of a single type of dicarboxyl monomer. In suchembodiments, the acid component may comprise at least about 90 mole %,at least about 92 mole %, at least about 95 mole %, at least about 97mole %, at least about 99 mole %, or 100 mole % of residues of a certaindicarboxyl monomer. Thus, the acid component may comprise not more thanabout 10 mole %, not more than about 8 mole %, not more than about 5mole %, not more than about 3 mole %, or not more than about 1 mole %,or 0 mole % of residues other than residues of a specified dicarboxylmonomer, based on the total residues of the acid component.

In some embodiments, one or both of the dicarboxyl monomers may bepresent in an amount of 5 to 60 mole %; 5 to 55 mole %; 5 to 50 mole %;5 to 45 mole %; 5 to 40 mole %; 5 to 35 mole %; 5 to 30 mole %; 5 to 25mole %; 5 to 20 mole %; 5 to 15 mole %; 10 to 60 mole %; 10 to 55 mole%; 10 to 50 mole %; 10 to 45 mole %; 10 to 40 mole %; 10 to 35 mole %;10 to 30 mole %; 10 to 25 mole %; 10 to 20 mole %; 15 to 60 mole %; 15to 55 mole %; 15 to 50 mole %; 15 to 45 mole %; 15 to 40 mole %; 15 to35 mole %; 15 to 30 mole %; 15 to 25 mole %; 20 to 60 mole %; 20 to 55mole %; 20 to 50 mole %; 20 to 45 mole %; 20 to 40 mole %; 20 to 35 mole%; 20 to 30 mole %; 25 to 60 mole %; 25 to 55 mole %; 25 to 50 mole %;25 to 45 mole %; 25 to 40 mole %; 25 to 35 mole %; 30 to 60 mole %; 30to 55 mole %; 30 to 50 mole %; 30 to 45 mole %; 30 to 40 mole %; 35 to60 mole %; 35 to 55 mole %; 35 to 50 mole %; 35 to 45 mole; 40 to 60mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 60 mole %; 45 to 55 mole%; or 50 to 60 mole %, while the other dicarboxyl monomer may be presentin an amount of 40 to 95 mole %; 40 to 90 mole %; 40 to 85 mole %; 40 to80 mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65 mole %; 40 to 60mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 95 mole %; 45 to 90 mole%; 45 to 85 mole %; 45 to 80 mole %; 45 to 75 mole %; 45 to 70 mole %;45 to 65 mole %; 45 to 60 mole %; 45 to 55 mole %; 50 to 95 mole %; 50to 90 mole %; 50 to 85 mole %; 50 to 80 mole %; 50 to 75 mole %; 50 to70 mole %; 50 to 65 mole %; 50 to 60 mole %; 55 to 95 mole %; 55 to 90mole %; 55 to 85 mole %; 55 to 80 mole %; 55 to 75 mole %; 55 to 70 mole%; 55 to 65 mole %; 60 to 95 mole %; 60 to 90 mole %; 60 to 85 mole %;60 to 80 mole %; 60 to 75 mole %; 60 to 70 mole %; 65 to 95 mole %; 65to 90 mole %; 65 to 85 mole %; 65 to 80 mole %; 65 to 75 mole %; 70 to95 mole %; 70 to 90 mole %; 70 to 85 mole %; 70 to 80 mole %; 75 to 95mole %; 75 to 90 mole %; 75 to 85 mole %; 80 to 95 mole %; 80 to 90 mole%, based on the total moles of the acid component.

Examples of dicarboxyl monomers used to form polyester polyols of thepresent invention can include, but are not limited to, isophthalic acid(or dimethyl isophthalate or esters thereof), terephthalic acid (ordimethyl terephthalate or esters thereof), phthalic acid or estersthereof, phthalic anhydride, 1,4-cyclohexane-dicarboxylic acid,1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride,tetrahydrophthalic anhydride, tetrachlorophthalic anhydride,dodecanedioic acid, sebacic acid, azelaic acid, maleic acid oranhydride, fumaric acid, succinic anhydride, succinic acid, adipic acid,dimer acid, hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid,glutaric acid, itaconic acid, and their derivatives, diglycolic acid;2,5-norbornanedicarboxylic acid; 1,4-naphthalenedicarboxylic acid;2,5-naphthalenedicarboxylic acid; diphenic acid; 4,4′-oxydibenzoic acid;4,4′-sulfonyidibenzoic acid, and mixtures thereof. In some embodiments,the dicarboxyl monomer may be selected from the group consisting of1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid,hexahydrophthalic anhydride, and combinations thereof.

In some embodiments, the acid component of the polyester polyol maycomprise residues of adipic acid. When present, the acid component maycomprise adipic acid residues in an amount of at least about 5 mole %,at least about 10 mole %, at least about 15 mole %, at least about 20mole %, at least about 25 mole %, at least about 30 mole %, at leastabout 35 mole %, at least about 40 mole %, at least about 45 mole %, orat least about 50 mole % and/or not more than about 95 mole %, not morethan about 90 mole %, not more than about 85 mole %, not more than about80 mole %, not more than about 75 mole %, not more than about 70 mole %,not more than about 65 mole %, not more than about 60 mole %, not morethan about 55 mole %, not more than about 50 mole %, or not more thanabout 45 mole %. In some embodiments, the acid component of thepolyester polyol may comprise not more than 10 mole %, not more thanabout 5 mole %, not more than about 2 mole %, or not more than about 1mole percent of residues other than adipic acid.

In some embodiments, the acid component of the polyester polyol maycomprise residues of isophthalic acid. When present, the acid componentmay comprise isophthalic acid residues in an amount of at least about 5mole %, at least about 10 mole %, at least about 15 mole %, at leastabout 20 mole %, at least about 25 mole %, at least about 30 mole %, atleast about 35 mole %, at least about 40 mole %, at least about 45 mole%, or at least about 50 mole % and/or not more than about 95 mole %, notmore than about 90 mole %, not more than about 85 mole %, not more thanabout 80 mole %, not more than about 75 mole %, not more than about 70mole %, not more than about 65 mole %, not more than about 60 mole %,not more than about 55 mole %, not more than about 50 mole %, or notmore than about 45 mole %. In some embodiments, the acid component ofthe polyester polyol may comprise not more than 10 mole %, not more thanabout 5 mole %, not more than about 2 mole %, or not more than about 1mole percent of residues other than isophthalic acid. In someembodiments, the acid component may comprise not more than 95, not morethan about 90, or not more than about 85 mole percent of isophthalicacid.

In some embodiments, the polyester polyol may have an acid componentthat comprises at least about 10 mole percent of residues of adipic acidand at least about 10 mole percent of residues of isophthalic acid and adiol component that comprises at least about 10 mole percent of residuesof diethylene glycol and at least 10 mole percent of residues of TACD.In some embodiments, the polyester polyol may have an acid componentcomprising about 30 to about 60 mole percent of residues of adipic acidand about 40 to about 70 mole percent of residues of isophthalic acid,based on the total moles of said acid component and a diol componentcomprising about 20 to about 75 mole percent of residues of diethyleneglycol and about 20 to about 75 mole percent of residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), based on the total molesof said diol component.

In some embodiments, the polyester polyol may have an acid componentcomprising about 5 to about 100 mole percent of residues of a dicarboxylmonomer selected from the group consisting of1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, andhexahydrophthalic acid, based on the total moles of said acid component,and wherein said diol component further comprises about 5 to about 95mole percent of residues of said at least one diol monomer is selectedfrom the group consisting of 1,4-cyclohexanedimethanol, neopentylglycol, and combinations thereof, based on the total moles of said diolcomponent, with the remaining residues of the diol component comprisingTACD.

In some embodiments, the polyester polyol may have a hydroxyl number inthe range of from about 15 to about 120 mg KOH/g and a glass transitiontemperature in the range of from about −25° C. to 30° C. The polyesterpolyol may have a hydroxyl number of about 15 to about 50 mg KOH/g and aglass transition temperature of about 10 to 55° C., or about 20 to 55°C. In other embodiments, the polyester polyol may have a Tg of −25° C.to 20° C., a hydroxyl number of 15 to 70 mg KOH/g, and a number averagemolecular weight of 1500 to 9000 g/mole. In other embodiments, thepolyester polyol may have a Tg of 0 to 70° C., a hydroxyl number of 15to 60 mg KOH/g, and a number average molecular weight of 2000 to 5500g/mole.

In some embodiments, the acid component of the polyester polyol maycomprise lower amounts of certain acids, as compared to conventionalpolyols. For example, in some embodiments, the acid component of thepolyester polyol may comprise not more than 25 mole %, not more thanabout 20 mole %, not more than about 15 mole %, not more than about 10mole %, not more than about 8 mole %, not more than about 5 mole %, notmore than about 3 mole %, not more than about 2 mole %, not more thanabout 1 mole %, or not more than about 0.5 mole % of residues ofaromatic dicarboxyl monomers, including, but not limited to,terephthalic acid or dimethyl terephthalate, based on the total moles ofthe acid component.

The resulting polyester polyol may exhibit certain properties that makeit particularly useful in adhesive compositions as described herein. Forexample, in some embodiments, the polyester polyol may have a hydroxylfunctionality of 2.1 or less. The hydroxyl functionality of a polyol canbe calculated according to the following formula: OHfunctionality=Mn*N/56100, wherein Mn is the number average molecularweight of the polyester polyol (measured by gel permeationchromatography (GPC) using polystyrene equivalent molecular weight), Nis the hydroxyl number of the polyester polyol, measured according toASTM E222-17. In some embodiments, the polyester polyol may have ahydroxyl functionality of less than 2.1, not more than about 2.05, notmore than about 2.01, not more than about 2.0, or not more than about1.99. In some cases, the polyester polyol as described herein may bethermoplastic and may not be thermosetting. The polyester polyol may nothave a hydroxyl functionality greater than 2.1, at least about 2.2, atleast about 2.25, at least about 2.3, at least about 2.35, at leastabout 2.4, at least about 2.45, or at least about 2.5.

According to some embodiments, the polyester polyol as described hereinmay have a glass transition temperature (Tg) in the range of from −70°C. to 150° C., determined by Differential Scanning calorimetry (DSC)using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of20° C./min.

The polyester polyol may have a Tg of at least about −70, at least about−65, at least about −60, at least about −55, at least about −50, atleast about −45, at least about −40, at least about −35, at least about−30, at least about −25, at least about −20, at least about −15, atleast about −10, at least about −5, at least about 0, at least about 5,at least about 10, at least about 15, at least about 20, or at leastabout 25° C. and/or not more than about 150, not more than about 145,not more than about 140, not more than about 135, not more than about130, not more than about 125, not more than about 120, not more thanabout 115, not more than about 110, not more than about 105, not morethan about 100, not more than about 95, not more than about 90, not morethan about 85, not more than about 80, not more than about 75, not morethan about 70, not more than about 65, not more than about 60, not morethan about 55, not more than about 50, not more than about 45, not morethan about 40, not more than about 35, not more than about 30, not morethan about 25, or not more than about 20° C.

The glass transition temperature (Tg) of polyester polyol may be from−70° C. to 120° C., from −60° C. to −20° C., from −40° C. to −10° C.,from −30° C. to 10° C., from −30° C. to 20° C., from −10° C. to 20°,from 0° C. to 30° C., from 20° C. to 50° C., from 30° C. to 60° C., from40° C. to 70° C., from 50° C. to 80° C., or from 60° C. to 100° C., orfrom −30 to 30° C., from −30 to 55° C., from −25 to 30° C., from −25 to25° C., from −25 to 25° C., from −25 to −20° C., from −20 to 20° C.,from −15 to 15° C., from −15 to 25° C., from −5 to 75° C., from 0 to 70°C., from 0 to 65° C., from 0 to 60° C., from 0 to 55° C., from 10 to 55°C., from −10 to 35° C., from −70° C. to 100° C., from −60° C. to −10°C., from −50° C. to −10° C., from −40° C. to −10° C., from −30° C. to−10° C., from 0° C. to 100° C., from 10° C. to 80° C., from 20° C. to70° C., from 30° C. to 70° C., from 40° C. to 70° C.

In some embodiments, the polyester polyol may have a Brookfieldviscosity, measured according to ASTM D3236 using a Brookfield DV-1Prime viscometer Thermosel™ and spindle 27 at the specified temperature(AMETEK Brookfield, Middleborough, Mass., US), in the range of fromabout 0.01 to 200 Pa·s, at 130° C. In some cases, the viscosity of thepolyester polyol at 130° C. may be at least about 0.01, at least about0.05, at least about 0.1, at least about 0.5, at least about 1, at leastabout 1.5, at least about 2, at least about 2.5, at least about 3, atleast about 3.5, at least about 4, at least about 4.5, at least about 5,at least about 5.5, at least about 6, at least about 6.5, at least about7, at least about 7.5, at least about 8, at least about 9, at leastabout 10, and/or not more than about 50, not more than about 45, notmore than about 40, not more than about 35, not more than about 30, notmore than about 27, not more than about 25, not more than about 20, ornot more than about 18 Pa·s. In some cases, the Brookfield viscosity ofthe polyester polyol may be from 0.01 to 50 Pa·s, from 0.1 to 40 Pa·s,from 1 to 35 Pa·s, or from 10 to 25 Pa·s.

In some embodiments, the polyester polyol may have a hydroxyl number inthe range of from 5 to 300 mg KOH/g, and/or an acid number of not morethan 50 mg KOH/g. Acid number is determined by the titration method inaccordance with ASTM D974. Hydroxyl number is determined by ASTME222-17.

In some embodiments, the polyester polyol may have a hydroxyl number ofat least about 5 mg KOH/g, at least about 10 mg KOH/g, at least about 15mg KOH/g, 20 mg KOH/g, 25 mg KOH/g, 30 mg KOH/g, 35 mg KOH/g, 40 mgKOH/g, 45 mg KOH/g, 50 mg KOH/g, 55 mg KOH/g, 60 mg KOH/g, 65, mg KOH/g,or 70 mg KOH/g. Additionally, or in the alternative, the polyesterpolyol may have a hydroxyl number of not more than about 300 mg KOH/g,not more than about 250 mg KOH/g, not more than about 200 mg KOH/g, notmore than about 150 mg KOH/g, not more than about 100 mg KOH/g, not morethan about 75 mg KOH/g, not more than about 70 mg KOH/g, not more thanabout 65 mg KOH/g, not more than about 60 mg KOH/g, not more than about55 mg KOH/g, not more than about 50 mg KOH/g, not more than about 45 mgKOH/g, or not more than about 40 mg KOH/g.

In some embodiments, the hydroxyl number of the polyester polyol may befrom about 10 to about 300, from about 10 to about 200, from about 10 toabout 180, or from about 10 to about 150, or from about 10 to about 120,or from about 10 to about 100, or from about 15 to about 100, from about25 to about 300, from about 25 to about 200, from about 25 to about 180,or from about 25 to about 150, or from about 25 to about 120, or fromabout 25 to about 100, or from 30 to about 300, from about 30 to about200, from about 30 to about 180, or from about 30 to about 150, or fromabout 30 to about 120, or from about 30 to about 100, or from about 50to about 300, from about 50 to about 200, from about 50 to about 180, orfrom about 50 to about 150, or from about 50 to about 120, or from about50 to about 100 mgKOH/g.

Additionally, or in the alternative, the polyester polyol can have ahydroxyl number of about 10 to about 60 mg KOH/g, about 10 to about 55mg KOH/g, about 10 to about 50 mg KOH/g, about 10 to about 45 mg KOH/g,about 15 to about 60 mg KOH/g, about 15 to about 55 mg KOH/g, about 15mg KOH/g to about 55 mg KOH/g, or about 15 to about 50 mg KOH/g, about15 to about 45 mg KOH/g, about 15 to about 35 mg KOH/g, or about 15 toabout 30 mg KOH/g.

In some embodiments, the polyester polyol may have an acid number of notmore than about 30 mg KOH/g, not more than about 25 mg KOH/g, not morethan about 20 mg KOH/g, not more than about 15 mg KOH/g, not more thanabout 10 mg KOH/g, or not more than about 5 mg KOH/g. In someembodiments, the acid number of the polyester polyol may be from 0 toabout 30, from about 3 to about 25, from 3 to about 15, or from 3 toabout 12, or from about 5 to about 25, from 5 to about 15, or from 5 toabout 12, or from about 8 to about 25, from 8 to about 15, or from 8 toabout 12 mgKOH/g. In some embodiments, the polyester polyol may have anacid number from about 0.5 to about 9.0, or from about 0.5 to about 8.0,or about 0.5 to about 7.0, or about 0.5 to about 6.0, or about 0.5 toabout 5.0, or about 0.5 to about 4.0, or about 0.5 to about 3.0, orabout 0.5 to about 2.

Equivalent ratio of OH/COOH of the polyester polyols described hereindenotes the ratio of total OH equivalents/total COOH equivalents. Incertain embodiments, the equivalent ratio (OH/COOH) of a polyesterpolyol as described herein may be from 1 to 3, or 1.1 to 3, or 1 to 2,or 1.1 to 2, or 1 to 1.5, or 1.1 to 1.5, or 1.0 to 1.3 or, 1.1 to 1.3.The polyester polyol may have an equivalent ratio of at least about 1,at least about 1.1, at least about 1.2, at least about 1.3, at leastabout 1.4, at least about 1.5, at least about 1.6, at least about 1.7,at least about 1.8, or at least about 1.9 and/or not more than about 3,not more than about 2.9, not more than about 2.8, not more than about2.7, not more than about 2.6, not more than about 2.5, not more thanabout 2.4, not more than about 2.3, or not more than about 2.2.

In some embodiments, the number average molecular weight (Mn) of thepolyester polyol may be from 500 to 10,000, or from 500 to 9,000, orfrom 500 to 8,000, or from 500 to 7,000, or from 500 to 6,000, or from500 to 5,000, or from 500 to 4,000, or from 500 to 3,000, or from 1,000to 10,000, or from 1,000 to 9,000, or from 1,000 to 8,000, or from 1,000to 7,000, or from 1,000 to 6,000, or from 1,000 to 5,000, or from 1,000to 4,000, or from 1,000 to 3,000, or from 2,000 to 7,000, or from 2,000to 6,000, or from 2,000 to 5,000, or from 2,000 to 4,000, or from 3,000to 7,000, or from 3,000 to 6,000, or from 3,000 to 5,000 g/mole.

The Mn of the polyester polyol may be at least about 500, at least about750, at least about 1000, at least about 1050, at least about 1100, atleast about 1150, at least about 1200, at least about 1250, at leastabout 1300, at least about 1350, at least about 1400, at least about1450, at least about 1500, at least about 1550, at least about 1600, atleast about 1650, at least about 1700, at least about 1750, at leastabout 1800, at least about 1850, at least about 1900, at least about1950, at least about 2000, at least about 2100, at least about 2200, atleast about 2300, at least about 2400, at least about 2500, at leastabout 2600, at least about 2700, at least about 2800, at least about2900, at least about 3000, at least about 3100, at least about 3200, atleast about 3300, at least about 3400, at least about 3500, at leastabout 3600, at least about 3700, at least about 3800, at least about3900, at least about 4000, at least about 4100, at least about 4200, atleast about 4300, at least about 4400, or at least about 4500 g/mole.

Additionally, or in the alternatively, the Mn of the polyester polyolmay be not more than about 10,000, not more than about 9900, not morethan about 9800, not more than about 9700, not more than about 9600, notmore than about 9500, not more than about 9400, not more than about9300, not more than about 9200, not more than about 9100, not more thanabout 9000, not more than about 8900, not more than about 8800, not morethan about 8700, not more than about 8600, not more than about 8500, notmore than about 8400, not more than about 8300, not more than about8200, not more than about 8100, not more than about 8000, not more thanabout 7900, not more than about 7800, not more than about 7700, not morethan about 7600, not more than about 7500, not more than about 7400, notmore than about 7300, not more than about 7200, not more than about7100, not more than about 7000, not more than about 6900, not more thanabout 6800, not more than about 6700, not more than about 6600, not morethan about 6500, not more than about 6400, not more than about 6300, notmore than about 6200, not more than about 6100, not more than about6000, not more than about 5900, not more than about 5800, not more thanabout 5700, not more than about 5600, or not more than about 5500g/mole.

The weight average molecular weight (Mw) of the polyester polyol may befrom 1,000 to 100,000, from 1,500 to 50,000, or from 1,500 to 15,000, orfrom 1,500 to 12,000, or from 2,000 to 10,000 g/mole. Molecular weightsare measured by gel permeation chromatography (GPC) using polystyreneequivalent molecular weight.

In some embodiments, the Mw of the polyester polyol may be from 500 to10,000, or from 500 to 9,000, or from 500 to 8,000, or from 500 to7,000, or from 500 to 6,000, or from 500 to 5,000, or from 500 to 4,000,or from 500 to 3,000, or from 1,000 to 10,000, or from 1,000 to 9,000,or from 1,000 to 8,000, or from 1,000 to 7,000, or from 1,000 to 6,000,or from 1,000 to 5,000, or from 1,000 to 4,000, or from 1,000 to 3,000,or from 2,000 to 7,000, or from 2,000 to 6,000, or from 2,000 to 5,000,or from 2,000 to 4,000, or from 3,000 to 7,000, or from 3,000 to 6,000,or from 3,000 to 5,000 g/mole.

The Mw of the polyester polyol may be at least about 500, at least about750, at least about 1000, at least about 1050, at least about 1100, atleast about 1150, at least about 1200, at least about 1250, at leastabout 1300, at least about 1350, at least about 1400, at least about1450, at least about 1500, at least about 1550, at least about 1600, atleast about 1650, at least about 1700, at least about 1750, at leastabout 1800, at least about 1850, at least about 1900, at least about1950, at least about 2000, at least about 2100, at least about 2200, atleast about 2300, at least about 2400, at least about 2500, at leastabout 2600, at least about 2700, at least about 2800, at least about2900, at least about 3000, at least about 3100, at least about 3200, atleast about 3300, at least about 3400, at least about 3500, at leastabout 3600, at least about 3700, at least about 3800, at least about3900, at least about 4000, at least about 4100, at least about 4200, atleast about 4300, at least about 4400, or at least about 4500 g/mole.

Additionally, or in the alternatively, the Mw of the polyester polyolmay be not more than about 10,000, not more than about 9900, not morethan about 9800, not more than about 9700, not more than about 9600, notmore than about 9500, not more than about 9400, not more than about9300, not more than about 9200, not more than about 9100, not more thanabout 9000, not more than about 8900, not more than about 8800, not morethan about 8700, not more than about 8600, not more than about 8500, notmore than about 8400, not more than about 8300, not more than about8200, not more than about 8100, not more than about 8000, not more thanabout 7900, not more than about 7800, not more than about 7700, not morethan about 7600, not more than about 7500, not more than about 7400, notmore than about 7300, not more than about 7200, not more than about7100, not more than about 7000, not more than about 6900, not more thanabout 6800, not more than about 6700, not more than about 6600, not morethan about 6500, not more than about 6400, not more than about 6300, notmore than about 6200, not more than about 6100, not more than about6000, not more than about 5900, not more than about 5800, not more thanabout 5700, not more than about 5600, or not more than about 5500g/mole.

In some embodiments, the polyester polyol may have an inherent viscosity(IV) less than longer-chain polyesters. For example, in someembodiments, the polyester polyol may have an IV of not more than about0.4 dL/g, measured in a 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.5 g/100 mL at 25° C. In some embodiments, thepolyester polyol may have an IV of at least about 0.01, at least about0.05, at least about 0.10, at least about 0.15, at least about 0.20, atleast about 0.25, at least about 0.30 dL/g and/or not more than about0.50, not more than about 0.45, not more than about 0.40, not more thanabout 0.35, not more than about 0.30, not more than about 0.25, or notmore than about 0.20 dL/g.

In some embodiments, a method for making a polyester polyol is providedthat includes reacting at least one dicarboxyl monomer with at least onediol comprising 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to form apolyester polyol as described herein. During the reacting step, thereaction medium may be heated so that the highest average temperature ofthe reaction medium reached is at least about 200, at least about 205,at least about 210, at least about 215, at least about 220, at leastabout 225, at least about 230, at least about 235, at least about 240,or at least about 245 and/or not more than about 300, not more thanabout 290, not more than about 280, not more than about 270, not morethan about 265, not more than about 260, not more than about 255, notmore than about 250, or not more than about 240° C.

Despite being conducted at lower-than-expected temperatures, thereaction medium used to form the polyester polyol may comprise little orno azeotroping solvent such as, for example, A150. In some cases, thereaction for forming the polyester polyol may be carried out in thepresence of not more than 20, not more than about 15, not more thanabout 10, not more than about 8, not more than about 5, not more thanabout 3, not more than about 2, not more than about 1, or not more thanabout 0.5 weight percent of an azeotroping solvent, based on the totalweight of the reaction medium.

All or a portion of the reaction may take place under vacuum so that,for example, the pressure can be at least about 5, at least about 10, atleast about 15, at least about 20, or at least about 25 torr and/or notmore than about 500, not more than about 450, not more than about 400,not more than about 350, not more than about 300, not more than about250, not more than about 200, not more than about 150, not more thanabout 100, or not more than about 75 torr. The reaction pressure can bein the range of from about 5 to about 200 torr, about 10 to about 150torr, or about 20 to about 100 torr.

In some embodiments, the reaction used to form the polyester polyol maybe carried out in the presence of at least one catalyst. In some cases,the catalyst may be present in an amount of at least about 0.1, at leastabout 0.5, at least about 1, at least about 1.5, or at least about 2weight percent and/or not more than about 20, not more than about 15,not more than about 10, not more than about 5, or not more than about 3weight percent, based on the total weight of the reaction medium.

In some embodiments, the catalyst may be present in the reaction mediumin an amount of at least about 5, at least about 10, at least about 15,at least about 20, at least about 30, at least about 40, at least about45, at least about 50, or at least about 55 parts per million by weight(ppmw) and/or not more than about 1000, not more than about 900, notmore than about 800, not more than about 700, not more than about 600,not more than about 500, not more than about 450, not more than about400, not more than about 350, not more than about 300, not more thanabout 250 ppmw, based on the total weight of the reaction medium.

Any suitable type of catalyst may be used, although in some embodiments,the catalyst may not be or comprise a tin-containing catalyst. In someembodiments, the catalyst may comprise not more than about 5, not morethan about 4, not more than about 3, not more than about 2, not morethan about 1, or not more than about 0.5 mole percent tin, based on thetotal weight of the catalyst, or it may include no tin. The catalyst mayinstead comprise titanium or other metal in an amount of at least about1, at least about 2, at least about 5, at least about 10, or at leastabout 25 mole percent and/or not more than about 90, not more than about85, not more than about 80, not more than about 75, or not more thanabout 70 mole percent, based on the total moles of the catalyst. In someembodiments, the catalyst can comprise titanium isopropoxide.

Polyester polyols according to embodiments of the present invention maybe particularly suitable for use in a variety of adhesive compositionsand, in particular, for use in polyurethane adhesive compositions.Polyurethane is formed by reacting a polyester polyol having hydroxylfunctionality with an isocyanate having two or more isocyanatefunctional groups. In some cases, at least a portion of this reactioncan occur prior to use of the adhesive so that, for example, theadhesive composition comprises an isocyanate-containing polyurethaneprepolymer. Alternatively, or in addition, the reaction may occur whilethe adhesive is being applied so that the polyurethane polymer is beingformed in situ on the substrate. Various embodiments of specific typesof adhesive compositions are discussed herein.

The amount of polyester polyol in the adhesive composition may varydepending on the specific application. In some embodiments, thepolyester may be present in the adhesive composition (or a precursorthereto) in an amount of at least about 2, at least about 5, at leastabout 10, at least about 15, at least about 20, at least about 25, atleast about 30, at least about 35, or at least about 40 weight percentand/or not more than about 90, not more than about 85, not more thanabout 80, not more than about 75, not more than about 70, not more thanabout 65, not more than about 60, not more than about 55, not more thanabout 50, or not more than about 45 weight percent, based on the totalweight of the adhesive composition.

The polyester polyol may be present in the adhesive composition alone,or in combination with one or more other polyols including, but notlimited to, various other polyester polyols or polyether polyols. Insome embodiments, particularly when the adhesive is a hot melt adhesive,the composition may include a blend of two or more polyols. In somecases, the polyols other than the TMCD-containing polyol may bepolyester polyols, polyether polyols, or combinations thereof.

When present in a blend, the polyester polyol comprising residues ofTMCD can be present in the composition in an amount of at least about 5,at least about 10, at least about 15, at least about 20, at least about25, at least about 30, at least about 35, at least about 40, at leastabout 45, at least about 50, at least about 55, at least about 60, atleast about 65, at least about 70 and/or not more than about 95, notmore than about 90, not more than about 85, not more than about 80, notmore than about 75, not more than about 70, not more than about 65, ornot more than about 60 weight percent, based on the total weight of theactive components. As used herein, the term “active components” refersto the components of an adhesive composition such as the polyol,isocyanate, and additives but does not include solvents or any inertcomponents.

In some embodiments, hot melt adhesives as described herein may includeat least one amorphous polyester polyol, a semi-crystalline polyesterpolyol, and/or a polyether polyol, in combination with the polyesterpolyol comprising residues of TMCD described herein. Examples ofamorphous polyols include, but are not limited to, high Tg amorphouspolyols such as, Dynacoll 7100 (commercially available from Evonik),Stepanpol PN-110 (commercially available from Stephan), and HS 2F-136Pand HS 2F-306P (commercially available from Hokoku Corporation). High Tgamorphous polyester polyols may be present in the adhesive blend in anamount of at least about 5, at least about 10, at least about 15 weightpercent and/or not more than about 50, not more than about 45, not morethan about 40, not more than about 35, or not more than about 30 weightpercent, based on the total weight of the composition.

Additionally, or in the alternative, the adhesive blend may alsocomprise at least one low Tg amorphous polyester polyol. Examples ofsuch a polyester polyol include, but are not limited to, Dynacoll 7200(commercially available from Evonik). Such polyols may be present in thecomposition in the same amount as described previously and may be usedalone or in combination with a higher Tg amorphous polyester.

In some embodiments, the adhesive blend may further comprise asemi-crystalline polyester polyol in combination with theTMCD-containing polyester polyol described herein. Examples of suchpolyester polyols can include, but are not limited to, Dynacoll 7300series polyols (commercially available from Evonik) PC-205P-30(commercially available from Stepan), and HS 2H-351A and HS2H-3505(commercially available from Hokoku Corporation). The amount ofsemi-crystalline polyester polyol may be 0, or at least about 5, atleast about 10, at least about 15, at least about 20, at least about 25,at least about 30, at least about 35 and/or not more than about 55, notmore than about 50, not more than about 45, not more than about 40, notmore than about 35, not more than about 30, or not more than about 25weight percent, based on the total weight of the composition. Theseranges may also apply to the amount of the TMCD-containing polyesterpolyol described herein in an adhesive composition.

Additionally, or in the alternative, the adhesive composition maycomprise at least one polyether polyol. Examples of suitable polyetherpolyols include, but are not limited to, Voranol 2120 and 2000LM(commercially available from Dow Chemical). In some embodiments, thepolyether polyol may be used in an amount of 0, or at least about 5, atleast about 10, at least about 15, at least about 20, at least about 25,at least about 30, at least about 35 and/or not more than about 55, notmore than about 50, not more than about 45, not more than about 40, notmore than about 35, not more than about 30, or not more than about 25weight percent, based on the total weight of the composition.

In some embodiments, the adhesive composition may only include thepolyester polyol including TMCD residues as described herein. In somecases, the adhesive composition may comprise not more than about 20, notmore than about 15, not more than about 10, not more than about 5, notmore than about 3, not more than about 2, not more than about 1, or notmore than about 0.5 weight percent of polyols other than theTMCD-containing polyol described herein, based on the total weight ofthe adhesive composition.

The adhesive composition may also include at least one isocyanate. Theisocyanate may comprise a diisocyanate and may be present in theadhesive composition (or a precursor thereto) in an amount of at leastabout 0.1, at least about 0.5, at least about 1, at least about 1.5, atleast about 2, at least about 2.5, at least about 5, at least about 8,at least about 10, at least about 15 and/or not more than about 50, notmore than about 45, not more than about 40, not more than about 35, notmore than about 30, not more than about 25, not more than about 20, notmore than about 15, not more than about 10, not more than about 8, notmore than about 5, not more than about 3, not more than about 1.5, notmore than about 1, or not more than about 0.5 weight percent, based onthe total weight of the adhesive composition (or its precursor).

Suitable isocyanates may be difunctional or multifunctional isocyanateshaving, for example, two or more isocyanate functional groups. Suchisocyanates may be aromatic or aliphatic. Examples of aliphaticisocyanates include isophorone diisocyanate (IPDI), hexamethylenediisocyanate (HDI), tetramethylene diisocyanate, methylenebis(4-cyclohexylisocyanate) (HMDI), m-xylylene diisocyanate, p-xylylenediisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, cyclohexylene diisocyanate,1,3-bis(1-isocyanato-1-methylethyl)benzene, HDI trimer, HDI biuret, HDIuretdione, IPDI trimer, and mixtures thereof. The isocyanate may alsocomprise dimers or trimers of any of the above compounds. Examples ofaromatic isocyanates include methylenediphenyl diisocyanate (MDI),polymeric MDI (PMDI), toluene diisocyanate (TDI), naphthalenediisocyanate, 4,4′-stilbene diisocyanate, and mixtures thereof.

According to some embodiments, the isocyanate may be selected from thegroup consisting of isophorone diisocyanate (IPDI), hexamethylenediisocyanate (HDI), tetramethylene diisocyanate, methylenebis(4-cyclohexylisocyanate) (HMDI), m-xylylene diisocyanate, p-xylylenediisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, cyclohexylene diisocyanate,1,3-bis(1-isocyanato-1-methylethyl)benzene, methylenediphenyldiisocyanate (MDI), polymeric MDI (PMDI), toluene diisocyanate (TDI),naphthalene diisocyanate, 4,4′-stilbene diisocyanate, and mixturesthereof. In some embodiments, the isocyanate is selected from the groupconsisting of hexamethylene diisocyanate (HDI) trimer, isophoronediisocyanate (IPDI) trimer, and combinations thereof. In otherembodiments, the isocyanate is selected from the group consisting of2,4′-methylene diphenyl diisocyanate (2,4-MDI), 4,4′-methylene diphenyldiisocyanate (4,4-MDI), and combinations thereof.

In some embodiments, modified isocyanates may be used. For example, insome embodiments, the isocyanate may be modified with acrylic groups.Modified isocyanates can include modified methylenediphenyl diisocyanateselected from the group consisting of a carbodiimide-modifiedmethylenediphenyl diisocyanate, an allophanate-modifiedmethylenediphenyl diisocyanate, a biuret-modified methylenediphenyldiisocyanate, and combinations thereof.

In some embodiments, the adhesive composition can have an R value in therange of from 0.5 to 4. As used herein, the “R” value is the equivalentratio of isocyanate groups to hydroxyl groups in a composition. In someembodiments, the R value can be at least about 0.75, at least about0.90, at least about 1, at least about 1.1, at least about 1.2, at leastabout 1.3, at least about 1.4, at least about 1.5, at least about 1.6,at least about 1.7, at least about 1.8, at least about 1.9, or at leastabout 2 and/or not more than about 4, not more than about 3.9, not morethan about 3.8, not more than about 3.7, not more than about 3.6, notmore than about 3.5, not more than about 3.4, not more than about 3.3,not more than about 3.2, not more than about 3.1, or not more than about3.

The adhesive composition may also include one or more other componentssuch as, for example, a tackifier. The tackifier may help improve theadhesive properties, including but not limited to the viscosity, wettingbehavior, adhesion, particularly to low energy surfaces, andviscoelastic behavior of the finished adhesive composition. Thetackifier resin selected may vary depending on the exact curablecomposition and the balance of properties needed in an application, suchas peel strength, shear strength, and tack.

Tackifier resins that may be present in the adhesive compositionsdescribed herein may include, but are not limited to, cycloaliphatichydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon resins,aromatically modified C5 resins (commercially available as Piccotac™resins, Eastman Chemical Company, TN, US), C9 hydrocarbon resins(commercially available as Picco™ resins, Eastman), pure monomer resins(e.g., copolymers of styrene with alpha-methyl styrene, vinyl toluene,para-methyl styrene, indene, and methyl indene) (commercially availableas Kristalex™ resins, Eastman), DCPD resins, dicyclopentadienebased/containing resins, cyclo-pentadiene based/containing resins,terpene resins (commercially available as Sylvares™ resins, AZ ChemHoldings, LP, Jacksonville, Fla., US), terpene phenolic resins, terpenestyrene resins, esters of rosin (commercially available as Permalyn™resins, Eastman), esters of modified rosins, liquid resins of fully orpartially hydrogenated rosins, fully or partially hydrogenated rosinesters (commercially available as Foral™ and Foralyn™ resins, Eastman),fully or partially hydrogenated modified rosin resins, fully orpartially hydrogenated rosin alcohols, fully or partially hydrogenatedC5 resins, fully or partially hydrogenated C5/C9 resins, fully orpartially hydrogenated DCPD resins (commercially available as Escorez®5000-series resin, ExxonMobil Chemical Company, TX, US), fully orpartially hydrogenated dicyclopentadiene based/containing resins, fullyor partially hydrogenated cyclo-pentadiene based/containing resins,fully or partially hydrogenated aromatically modified C5 resins, fullyor partially hydrogenated C9 resins (commercially available as Regalite™resins, Eastman), fully or partially hydrogenated pure monomer resins(e.g., copolymers or styrene with alpha-methyl styrene, vinyl toluene,para-methyl styrene, indene, and methyl indene) (commercially availableas Regalrez™ resins, Eastman), fully or partially hydrogenatedC5/cycloaliphatic resins (commercially available as Eastotac™ resins,Eastman), fully or partially hydrogenated C5/cycloaliphatic/styrene/C9resins, fully or partially hydrogenated cycloaliphatic resins, andmixtures thereof.

When present, the tackifier may also include, for example, rosin esters,such as glycerol rosin ester, pentaerythritol rosin ester, andhydrogenated rosin resins, and hydrocarbon resins.

In some embodiments, the adhesive composition may include at least about5, at least about 10, at least about 15, at least about 20, or at leastabout 25 and/or not more than about 50, not more than about 45, not morethan about 40, not more than about 35, not more than about 30, or notmore than about 25 weight percent of at least one tackifier. In somecases, the adhesive composition may comprise less than about 5, lessthan about 3, less than about 2, less than about 1, or less than about0.5 weight percent of tackifiers, based on the total weight of thecomposition.

Additionally, or in the alternative, the adhesive composition mayfurther comprise one or more reactive or non-reactive vinyl polymers tofurther improve the desirable properties such as cure time, bondstrength, cohesion, and mechanical strength. Examples of such vinylpolymers include homopolymers and copolymers of ethylenicallyunsaturated monomers selected from the group comprising methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,butyl methacrylate, isobutyl acrylate, isobutyl methacrylate,2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octylacrylate, octyl methacrylate, iso-octyl acrylate, iso-octylmethacrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate,hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate, hydroxylbutyl (meth)acrylate, acetoacetoxy ethylmethacrylate, acetoacetoxy ethyl acrylate, methyl2-(hydroxymethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, isopropyl2-(hydroxymethyl)acrylate, n-butyl 2-(hydroxymethyl)acrylate, t-butyl2-(hydroxymethyl)acrylate, vinyl ester such as vinyl acetate, vinylalcohol, vinyl ether, styrene, alkylstyrene, butadiene, andacrylonitrile. The reactive vinyl polymers can have functionalities suchas, for example, hydroxyl, acetoacetate, and carbamate that are reactivetoward isocyanates, or they may have isocyanate functionality that ismoisture curable. The vinyl polymers may be used in various adhesiveformulations including solvent-borne, solventless, and hot melt types.

In some embodiments, the adhesive of the present invention may furthercomprise one or more catalysts or activating agents selected from thegroup comprising dibutyl tin dilaurate, dibutyl tin diacetate, dioctyltin diacetate, 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene (DBN),1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD),1,1,3,3-tetramethylguanidine (TMG), 1,4-diazabicyclo[2.2.2]octane(DABCO), 2,2′-di morpholinodieethylether (DMDEE), and combinationsthereof.

In some embodiments, the adhesive composition may be a two part ortwo-pack (also called a two-component or 2K) adhesive system. Suchsystems include two separate components or portions, one including thepolyol and the other including the isocyanate. These components arestored separately, then combined just prior to or during application ofthe adhesive, at which point the polyol and isocyanate react to form apolyurethane in situ. Such reactions can occur at room temperature or atan elevated temperature. One or both of the components may include othercompounds such as, for example, solvents or other additives.

In some embodiments, the polyol may be pre-reacted with an isocyanate toprovide an isocyanate-terminated polyurethane prepolymer. Thepolyurethane prepolymer may be prepared by bulk polymerization orsolution polymerization. The reaction may be carried out under anhydrousconditions to prevent crosslinking of the isocyanate groups by moisture.The polyurethane prepolymer may comprise residues of at least onepolyester polyol as described herein and at least one isocyanate.

This isocyanate-functional prepolymer, present in one component of theadhesive, may then be reacted further with a polyol, in anothercomponent, when part of a two-component (2K) adhesive composition. Insome embodiments, one or both parts of the 2K adhesive may furtherinclude at least one solvent. A 2K solvent-borne adhesive can be used inapplications for, for example, flexible packaging, textile, autointerior, wood working, assembly of electronic components, and pottingfor electronics.

Examples of suitable solvents can include, but are not limited to, ethylacetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propylacetate, isopropyl acetate, methyl acetate, ethanol, n-propanol,isopropanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether,propylene glycol n-butyl ether, propylene glycol methyl ether, propyleneglycol monopropyl ether, dipropylene glycol methyl ether, diethyleneglycol monobutyl ether, ethyl-3-ethoxypropionate, xylene, toluene,acetone, methyl amyl ketone, methyl isoamyl ketone, methyl ethyl ketone,cyclopentanone, and cyclohexanone.

When a solvent is present, the adhesive may have a solids content of atleast about 10, at least about 15, at least about 20, at least about 25,at least about 30, at least about 35, at least about 40, or at leastabout 45 weight percent and/or less than about 90, not more than about85, not more than about 80, not more than about 75, not more than about70, not more than about 65, not more than about 60, not more than about55, not more than about 50, or not more than about 45 percent, based onthe total weight of the adhesive composition.

Alternatively, the isocyanate-terminated polyurethane prepolymer mayreact with moisture (added or in the environment) at the time theadhesive is applied. Such moisture-cure adhesive compositions may beconsidered one-part (1K) adhesive compositions. Although not wishing tobe bound by theory, it is assumed that, in such moisture-cure systems,the isocyanate functionality of the polyurethane prepolymer first reactswith water to yield an amine functional compound, which then furtherreacts with the isocyanate group on another polymer molecule. A 1Kmoisture-cure adhesive can have utility in, for example, auto exterior,building and construction, textiles, wood working, assembly ofelectronic components, and potting for electronics.

In some embodiments, the adhesive composition can be a hot melt adhesiveor a reactive hot melt adhesive composition. When the adhesive is a hotmelt, it may comprise a solventless or solid composition and may beheated during all or a portion of its application. When the adhesivecomposition is solventless, it may have a solids content of at leastabout 90, at least about 92, at least about 95, at least about 97, atleast about 99, or at least about 99.5 weight percent, based on thetotal weight of the adhesive. Solventless adhesives may be in the formof pellets, powders, sticks, or other masses solid at room temperatureand pressure.

When the adhesive composition is a hot melt (or reactive hot melt)adhesive, it may be applied by heating the adhesive to a temperature ofat least about 50, at least about 55, at least about 60, at least about65, at least about 70, at least about 75, at least about 80, at leastabout 85, at least about 90, at least about 95, at least about 100, atleast about 105, at least about 110, at least about 115, at least about120, at least about 125, at least about 130, at least about 135, or atleast about 140° C. and/or not more than about 200, not more than about195, not more than about 190, not more than about 185, not more thanabout 180, not more than about 175, not more than about 170, not morethan about 165, not more than about 160, not more than about 155, or notmore than about 150° C. Hot melt adhesive compositions according toembodiments of the invention can be single component or two-componentadhesives. Typical methods of applying the hot melt adhesive include,but are not limited to, a roll coater, sprayer, or a glue gun.

Adhesive compositions as described herein may have enhanced propertiesas compared to adhesives formulated with conventional polyols. Forexample, adhesive compositions according to embodiments of the presentinvention may have both greater initial bond strength (offline bondstrength), as well as higher levels of both thermal and chemicalresistance. This makes the adhesives suitable for a variety of end useapplications, from woodworking to electronics to flexible packaging andautomotive finishes. Such adhesives exhibit high offline bond strength,quickly reach substrate failure, have a high chemical and thermalresistance, while avoiding polyols including certain monomers, whileachieving these properties with various isocyanates and on multiplelaminate structures.

In some embodiments, adhesive compositions as described herein may havean offline bond strength in the range of from 100 to 1000 grams per inch(g/in). Offline Bond Strength is measured according to ASTM F904-16immediately after lamination according to the procedure described inExample 3. The offline bond strength exhibited by the present inventioncan be at least about 150, at least about 200, at least about 250, atleast about 300, at least about 350, at least about 400, at least about450, at least about 500, or at least about 550 and/or not more thanabout 1000, not more than about 950, not more than about 900, not morethan about 850, not more than about 800, not more than about 750, notmore than about 700, not more than about 650, or not more than about 600g/in.

In some embodiments, the offline bond strength of the adhesivecomposition can be at least about 5, at least about 10, at least about15, at least about 20, at least about 25, at least about 30, at leastabout 35, at least about 40, at least about 45, at least about 50, atleast about 55, at least about 60, at least about 65, at least about 70,at least about 75, at least about 80 percent, or at least about 90percent higher than an identical adhesive composition formed with apolyester polyol having an acid component comprising 58 mole % adipicacid (AD) and 42 mole % isophthalic acid (IPA) and a diol componentcomprising 25 mole % diethylene glycol (DEG) and 75 mole % ethyleneglycol with a hydroxyl number of 24 KOH/g, and a glass transitiontemperature of −21° C., all other components of said adhesivecomposition being the same.

Alternatively, or in addition, the offline bond strength of the adhesivecomposition can be at least about 5, at least about 10, at least about15, at least about 20, at least about 25, at least about 30, at leastabout 35, at least about 40, at least about 45, at least about 50, atleast about 55, at least about 60, at least about 65, at least about 70,at least about 75, at least about 80 percent, or at least about 90percent higher than an identical adhesive composition formed with apolyester polyol that has an acid component comprising 50 mole %terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) and a diolcomponent comprising 52 mole % neopentyl glycol (NPG) and 48 mole %ethylene glycol with a hydroxyl number of 45 mg KOH/g, a glasstransition temperature of 50° C., and a melt viscosity of 130° C. at 60Pa, all other components being the same.

Adhesive compositions as described herein may have a 24-hour bondstrength, measured as described in Example 4, in the range of from about200 to about 3000 g/in. The 24-hour bond strength of the adhesivecomposition can be at least about 250, at least about 300, at leastabout 350, at least about 400, at least about 450, at least about 500,at least about 550, at least about 600, at least about 650, at leastabout 700, at least about 750, at least about 800, at least about 850,at least about 900, at least about 950, at least about 1000, at leastabout 1050, at least about 1100, at least about 1150, or at least about1200 and/or not more than about 3000, not more than about 2500, not morethan about 2000, not more than about 1500, not more than about 1000, notmore than about 950, not more than about 900, not more than about 850,not more than about 800, not more than about 750, or not more than about700 g/in.

In some embodiments, the 24 hour bond strength of the adhesivecomposition can be at least about 5, at least about 10, at least about15, at least about 20, at least about 25, at least about 30, at leastabout 35, at least about 40, at least about 45, at least about 50, atleast about 55, at least about 60, at least about 65, at least about 70,at least about 75, at least about 80 percent, or at least about 90percent higher than an identical adhesive composition formed with apolyester polyol having an acid component comprising 58 mole % adipicacid (AD) and 42 mole % isophthalic acid (IPA) and a diol componentcomprising 25 mole % diethylene glycol (DEG) and 75 mole % ethyleneglycol with a hydroxyl number of 24 KOH/g, and a glass transitiontemperature of −21° C., all other components of said adhesivecomposition being the same.

Additionally, or in the alternative, the 24 hour bond strength of theadhesive composition can be at least about 5, at least about 10, atleast about 15, at least about 20, at least about 25, at least about 30,at least about 35, at least about 40, at least about 45, at least about50, at least about 55, at least about 60, at least about 65, at leastabout 70, at least about 75, at least about 80 percent, or at leastabout 90 percent higher than an identical adhesive composition formedwith a polyester polyol that has an acid component comprising 50 mole %terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) and a diolcomponent comprising 52 mole % neopentyl glycol (NPG) and 48 mole %ethylene glycol with a hydroxyl number of 45 mg KOH/g, a glasstransition temperature of 50° C., and a melt viscosity of 130° C. at 60Pa, all other components being the same.

In some embodiments, the adhesive composition may have a chemicalresistance, measured as described in Example 5, in the range of 200 to1000 g/in, measured after boil-in-bag with 1:1:1 food simulant. Theadhesive composition can have a chemical resistance after boil-in-bagwith 1:1:1 food simulant can be at least about 250, at least about 300,at least about 350, at least about 400, at least about 450, or at leastabout 500 and/or not more than about 1000, not more than about 950, notmore than about 900, not more than about 850, not more than about 800,not more than about 750, not more than about 700, not more than about650, or not more than about 600 g/in.

Such a chemical resistance may be at least about 5, at least about 10,at least about 15, at least about 20, at least about 25, at least about30, at least about 35, at least about 40, at least about 45, at leastabout 50, at least about 55, at least about 60, at least about 65, atleast about 70, at least about 75, at least about 80 percent, or atleast about 90 percent higher than an identical adhesive compositionformed with a polyester polyol having an acid component comprising 58mole % adipic acid (AD) and 42 mole % isophthalic acid (IPA) and a diolcomponent comprising 25 mole % diethylene glycol (DEG) and 75 mole %ethylene glycol with a hydroxyl number of 24 KOH/g, and a glasstransition temperature of −21° C., all other components of said adhesivecomposition being the same.

Alternatively, or in addition, the chemical resistance of the adhesivecomposition can be at least about 5, at least about 10, at least about15, at least about 20, at least about 25, at least about 30, at leastabout 35, at least about 40, at least about 45, at least about 50, atleast about 55, at least about 60, at least about 65, at least about 70,at least about 75, at least about 80 percent, or at least about 90percent higher than an identical adhesive composition formed with apolyester polyol that has an acid component comprising 50 mole %terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) and a diolcomponent comprising 52 mole % neopentyl glycol (NPG) and 48 mole %ethylene glycol with a hydroxyl number of 45 mg KOH/g, a glasstransition temperature of 50° C., and a melt viscosity of 130° C. at 60Pa, all other components being the same.

In some embodiments, the adhesive composition may exhibit a thermalresistance of 200 to 800 g/in at 90° C., measured as described inExample 6. The thermal resistance of the adhesive composition can be atleast about 250, at least about 300, at least about 350, at least about400, at least about 450, at least about 500 and/or not more than about800, not more than about 750, not more than about 700, not more thanabout 650, not more than about 600, or not more than about 550 g/in.

Such a thermal resistance may be at least about 5, at least about 10, atleast about 15, at least about 20, at least about 25, at least about 30,at least about 35, at least about 40, at least about 45, at least about50, at least about 55, at least about 60, at least about 65, at leastabout 70, at least about 75, at least about 80 percent, or at leastabout 90 percent higher than an identical adhesive composition formedwith a polyester polyol having an acid component comprising 58 mole %adipic acid (AD) and 42 mole % isophthalic acid (IPA) and a diolcomponent comprising 25 mole % diethylene glycol (DEG) and 75 mole %ethylene glycol with a hydroxyl number of 24 KOH/g, and a glasstransition temperature of −21° C., all other components of said adhesivecomposition being the same.

Additionally, or in the alternatively, the adhesive composition canexhibit a thermal resistance that is at least about 5, at least about10, at least about 15, at least about 20, at least about 25, at leastabout 30, at least about 35, at least about 40, at least about 45, atleast about 50, at least about 55, at least about 60, at least about 65,at least about 70, at least about 75, at least about 80 percent, or atleast about 90 percent higher than an identical adhesive compositionformed with a polyester polyol that has an acid component comprising 50mole % terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) anda diol component comprising 52 mole % neopentyl glycol (NPG) and 48 mole% ethylene glycol with a hydroxyl number of 45 mg KOH/g, a glasstransition temperature of 50° C., and a melt viscosity of 130° C. at 60Pa, all other components being the same

In some cases, the adhesive composition may exhibit a time to achievesubstrate failure of less than 24 hours, measured as described inExample 4. The time to achieve substrate failure is the amount of timerequired for the adhesive to cure at 50° C. before substrate failureoccurs. In some cases, the time to substrate failure is not more than20, 15, 12, 10, 5, or 2 hours, and sometimes it occurs without curingthe adhesive (offline peel testing).

In some embodiments, the adhesive composition may exhibit one or more ofthe above properties. For example, the adhesive composition may have anoffline bond strength within one or more of the above ranges, as well a24-hour bond strength, offline bond strength, chemical resistance,thermal resistance, and time to substrate failure within one or more ofthe above ranges. In some cases, the adhesive composition exhibitsvalues within the above ranges for one, two, three, four, or five of theabove properties.

In some embodiments, adhesive compositions formed as described hereinmay exhibit a lower reduction in bond strength than would be expectedfrom a conventional adhesive. For example, in some embodiments, theadhesive composition comprising CHDM-containing polyester polyols canhave a reduction in bond strength of not more than 50, not more thanabout 45, not more than about 40, not more than about 35, not more thanabout 30, or not more than about 25 percent, measured according to thefollowing formula: (Bond Strength Before Curing−Bond Strength AfterCuring)/(Bond Strength Before Curing), expressed as a percentage. Asdescribed herein, the bond strength after curing measured for thereduction in bond strength is measured after 2 weeks of curing at atemperature of 85° C. and 85% relative humidity.

Additionally, the adhesive compositions described herein may reach abond strength of 75 psi in less than 20, less than 18, less than 16,less than 12, less than 10, or less than 8 minutes of curing at roomtemperature.

In some embodiments, the bond strength of the adhesive compositiondescribed herein may be greater than about 90, at least about 95, atleast about 100, at least about 110, at least about 120, at least about130, at least about 140, at least about 150, at least about 160, atleast about 170, at least about 180, at least about 190, at least about200, at least about 210, at least about 220, at least about 230, atleast about 240, at least about 250, at least about 260, at least about270, at least about 280, at least about 290, or at least about 300 psi,measured after curing the adhesive at room temperature for 2 weeks andthen heating to 82° C. for 30 minutes.

Further, in some embodiments, the adhesive compositions described hereinare visually transparent or translucent, rather than opaque.

Additionally, in some embodiments, the adhesive composition can includea Zahn #2 viscosity of less than about 25 seconds, less than about 24seconds, less than about 23, less than about 22, less than about 21,less than about 20, less than about 19, less than about 18, less thanabout 17, less than about 16, or less than about 15 seconds. Theadhesive composition may also have a pot life of at least about 6, atleast about 6.5, at least about 7, at least about 7.5, at least about 8,at least about 8.5, at least about 9, or at least about 9.5 hours.

According to embodiments of the present invention, there is provided amethod of using the adhesive compositions described herein. The methodcomprises contacting a surface of at least one layer or substrate withat least a portion of an adhesive composition, then adhering anotherlayer or substrate to the first via the adhesive layer. The adhesivecomposition used to form the adhesive layer may be any adhesivecomposition as described herein and can, in some cases, be a 1K or 2Kadhesive composition.

Additionally, there is provided a laminated article formed from anadhesive described herein comprising a first substrate presenting afirst surface, a second substrate presenting a second surface, and anadhesive layer disposed between and partially in contact with at leastone of the first and second surfaces. Each of the first and secondlayers may comprise a material selected from the group consisting ofpolyethylene terephthalate, polypropylene, aluminum-coated oraluminum-laminated polyethylene terephthalate, low density polyethylene,and combinations thereof. In some cases, the first and second layers maybe the same, while, in other embodiments, the first and secondsubstrates or layers may be different (or formed from differentmaterials).

In some embodiments, one or both of the first and second layers may havea thickness of at least about 0.5, at least about 1, at least about 1.5,or at least about 2 mil and/or not more than about 10, not more thanabout 8, not more than about 5, not more than about 3, not more thanabout 2, or not more than about 1.5 mil. The laminated article mayfurther comprise a third, fourth, fifth, or even sixth layer, eachseparated from and in contact with, at least one additional adhesivelayer, at least one of which is formed from an adhesive composition asdescribed herein.

In some embodiments, the laminated article, or film, may be used to formanother article such as, for example, a package, pouch, bag, or othertype of container for holding and storing at least one substance, suchas, for example, an edible item. The package, pouch, bag, or othercontainer may then be filled with at least one substance, such as, forexample, a foodstuff, beverage, or other edible substance, which canthen be sealed within the interior volume of the package. As discussedpreviously, such a package may exhibit enhanced chemical and thermalresistance to delamination or other types of failure, due to theenhanced performance of the adhesive used to form the laminate.

In another embodiment, there is provided a laminated article comprisinga first substrate presenting a first surface, a second substratepresenting a second surface, and an adhesive layer disposed between andin contact with at least a portion of the first and second surfaces. Thesubstrates may be selected from the group consisting of polymers(including, but not limited to, polymeric foams and thicker or rigidpolymeric substrates such as polycarbonate), wood, metal, fabric,leather, and combinations thereof. The first and second substrates maybe formed from the same material or each may be formed from a differentmaterial.

In some embodiments, the first and second substrates may have differentthicknesses such that, for example, one substrate is relatively thick(e.g., 0.25 inches or more), while the other is relative thin (e.g., notmore than 30 mils). Such differences in thickness may occur when, forexample, an adhesive composition is used to adhere an outer decorativeor functional layer to a base substrate. In some cases, the ratio of thethickness of the thinner substrate to the thicker substrate can be atleast about 0.0001:1, at least about 0.0005:1, at least about 0.001:1,at least about 0.005:1, at least about 0.01:1, at least about 0.05:1, atleast about 0.1:1, at least about 0.5:1, or at least about 0.75:1.

Examples of suitable end use applications for adhesives as describedherein can include, but are not limited to, woodworking, automotive,textile, appliances, electronics, book-binding, and packaging.

It is contemplated that compositions useful in the invention can possessat least one of the Tg ranges described herein and at least one of themonomer ranges for the compositions described herein unless otherwisestated. It is also contemplated that compositions useful in theinvention can possess at least one of the inherent viscosity rangesdescribed herein, at least one of the Tg ranges described herein, and atleast one of the monomer ranges for the compositions described herein,unless otherwise stated.

The following examples further illustrate how the polyesters in theinvention can be made and evaluated, and how the polyurethane adhesivescan be made and evaluated and are intended to be purely exemplary of theinvention and are not intended to limit the scope thereof. Unlessindicated otherwise, parts are parts by weight, temperature is indegrees C. (Celsius) or is at room temperature, and pressure is at ornear atmospheric.

EXAMPLES Example 1

A 12-L round bottom kettle with a four-neck lid was equipped with amechanical stirrer, a thermocouple, a heated partial condenser (100°C.), a Dean-Stark trap, and a chilled condenser (15° C.). The kettle wascharged with 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) (1890 g),diethylene glycol (DEG g), isophthalic acid (IPA) (2558 g), adipic acid(AD) (1098 g). The mixture was allowed to react under a nitrogenblanket. The temperature was increased from room temperature to 140° C.over 80 minutes. Once at 140° C., the temperature was then increasedfrom 140 to 250° C. over 4 hours. Once the maximum temperature wasreached, the acid catalyst, titanium isopropoxide (3.7 g), was added toreaction, vacuum of 28 torr was applied and the temperature was helduntil a low acid number was achieved. The polyester polyol was sampledfor acid number and achieved an acid number of 1.6. Then, the polyesterpolyol was allowed to cool to 190° C. before being poured into aluminumpans to further cool and a solid product collected.

Several polyester polyols having various compositions were synthesizedusing the same procedure. The compositions of each of these polyols arelisted in Table 1, where AD is adipic acid, IPA is isophthalic acid, DEGis diethylene glycol. All monomers are reported in mole %, where thediacids total 100 mole % and the diols total 100 mole %. Table 1 alsolists the respective polyol properties, in which Mn is the numberaverage molecular weight (g/mol), Mw is weight average molecular weight(g/mol), OHN is the hydroxyl number (mg KOH/g) and AN is the acid number(mg KOH/g).

TABLE 1 AD IPA DEG TMCD Sample (mol %) (mol %) (mol %) (mol %) OHN ANM_(n) M_(w) Polyol A1 33 67 79 21 21 3 5,700 13,000 Polyol B1 58 42 7921 19 2 4,800 14,000 Polyol C1 33 67 50 50 20 1 6,600 16,000 Polyol D158 42 50 50 17 0 6,600 16,000 Polyol E1 45 55 65 35 19 0 6,300 15,000Polyol F1 58 42 75 25 18 2 7,100 17,000 Polyol G1 58 42 60 40 19 1 6,00016,000 Polyol Z 58 42 25 75 10 2 8,000 22,000

Example 2

A 12-L round bottom kettle with a four-neck lid was equipped with amechanical stirrer, a thermocouple, a heated partial condenser (100°C.), a Dean-Stark trap, and a chilled condenser (15° C.). The kettle wascharged with 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) (1890 g),diethylene glycol (DEG g), isophthalic acid (IPA) (2558 g), adipic acid(AD) (1098 g). The mixture was allowed to react under a nitrogenblanket. The temperature was increased from room temperature to 140° C.over 80 minutes. Once at 140° C., the temperature was increased from 140to 250° C. over 4 hours. Then the acid catalyst, titanium isopropoxide(3.7 g), was added to reaction, vacuum of 28 torr was applied and thetemperature held until the polyol had an acid number of 1.6. Theresulting polyester polyol was allowed to cool to 190° C. before beingpoured into aluminum pans, wherein it was further cooled and collectedas a solid product.

Several polyester polyols having various compositions were synthesizedusing the same procedure. The compositions of each of these polyols arelisted in Table 2, where AD is adipic acid, IPA is isophthalic acid, DEGis diethylene glycol. All monomers are reported in mol %, where thediacids total 100% and the diols total 100%. Table 2 also lists glasstransition temperature (T_(g)) and the hydroxyl number (OHN) of therespective polyols.

Glass transition temperature was determined using a TA Instruments Q2000Differential Scanning calorimeter with the RCS-90 cooler and purged with50 mL/min N2. The sample was cooled to −55° C. then heated at 20° C./minto 205° C. It then equilibrated at 200° C. and held isothermally for 2minutes. The sample was then cooled again to −55° C. at 20° C./min thenequilibrated at −50° C. and held isothermally for 30 seconds. Finally,the sample was heated again at 20° C./min to 205° C.

Viscosity was determined using a Brookfield DV-1+viscometer that used aS28 spindle and ran at 100 rpm with 13.6% torque.

TABLE 2 Viscosity AD IPA DEG TMCD T_(g) Weight % 25° C. Polyol (mol %)(mol %) (mol %) (mol %) OHN (° C.) Solids (cP) Polyol-A1 33 67 79 21 21−5 — — Polyol-B1 58 42 79 21 19 −23 — — Polyol-C1 33 67 50 50 21 11 — —Polyol-C2 33 67 50 50 20 13 60 700 Polyol-D1 58 42 50 50 17 −8 — —Polyol-E1 45 55 65 35 19 −7 — — Polyol-F1 58 42 75 25 18 −20 — —Polyol-G1 58 42 60 40 19 −15 — — Polyol-Z 58 42 25 75 10 4 — — Polyol-C433 67 50 50 63 −3 — — Polyol-C5 33 67 50 50 102 −16 — — Polyol-A2 33 6779 21 19 −4 — — Polyol-D2 58 42 50 50 20 −8 — — Polyol-C3 33 67 50 50 2110 — —

Example 3

Polyol-A2 described in Example 2 was weighed into an 8 oz glass jarsthat has a Teflon lid with Urethane Grade Ethyl Acetate, making a polyolsolution of 60 wt % solids. The jar was closed and sealed withelectrical tape and rolled over night to allow for complete mixing. Whenready to coat, the polyol solution, the hardener, ethyl acetate, and anadhesion promoter was combined into another 8 oz glass jar and rolled tomix, making an adhesive formulation with 40 wt % solids and anisocyanate/OH index of 2.

The adhesive formulation was coated onto PET1 using a TMI AutomaticDrawdown Machine, Model KCC-101 and a Meyer rod #1 at 30 ft/min. Thecoated PET1 was placed in an oven at 65° C. for 1 minute. The secondfilm, CPP, after treated by a corona treater at a watt density of 10KWf²/m, is then placed on top of the coated PET1, and the structure islaminated using a laminator (Scotch® TL806 Smart Thermal Laminator,Office Depot). This results in a laminated film with a (dry) coat weightof about 4 gsm (grams per square meter). See Table 3, below, for furtherdetails on the types of substrates.

Polyol-A1, pre-diluted with Urethane Grade Ethyl Acetate to 60 wt %solids, was poured into a plastic bucket. HDI trimer, pre-diluted withUrethane Grade Ethyl Acetate to 20 wt % solids, ethyl acetate, andadditional components, such as an adhesion promoter, were poured intothe same bucket, and mixed into an adhesive formulation of 39 wt %solids. It had an isocyanate/OH index of 2 and a Zahn #2 viscosity of 22seconds.

The adhesive formulation was then poured into the gravure pan of aFaustel LabMaster pilot line laminator. The adhesive formulation wascoated onto PET-Al with a gravure coating roll of 120 LPI/15 BCM at aline speed of 50 ft/min. The coated PET-Al was then sent through a 10 ftdryer, heated to 175° F. After the coated PET-Al leaves the dryer, CPPpretreated by corona, was placed on top of the coated PET-Al and putthrough a laminating roll heated to 170° F. and under 65 psi ofpressure.

Next the viscosity of the adhesive compositions was measured with a #2Zahn cup according to ASTM D4212 “Standard Test Method for Viscosity byDip-Type Viscosity Cups.” Table 3 below summarizes specifics regardingeach of the tested substrates, monomers, and hardeners. Tables 4 and 5below summarize the results of testing of the above adhesivecompositions.

TABLE 3 Flexible Substrates (Films): PET1 Polyethylene terephthalate, 1mil (Mitsubishi), surface treated by supplier, used for hand laminationsPET2 Polyethylene terephthalate, 1 mil (Neologic Solutions), coronatreated prior to use, used for machine laminations CPP1 Castpolypropylene, 2 mil (Neologic), corona treated prior to use, used forhand laminations CPP2 Cast polypropylene, 2 mil (Berry), corona treatedprior to use, used for machine laminations PET-Al Al foil/PET laminate,32 micron (Neologic solutions), corona treated prior to use, used formachine laminations LDPE Low density polyethylene, 1.5 mil (Berry),corona treated prior to use, used for machine laminations Monomers: ADadipic acid IPA isophthalic acid TMCD2,2,4,4-tetramethyl-1,3-cyclobutanediol DEG diethylene glycol IsocyanateHardeners: HDI Trimer hexamethylene diisocyanate trimer IPDI Trimerisophorone diisocyanate trimer

TABLE 4 AD IPA DEG TMCD EG T_(g) Polyol (mol %) (mol %) (mol %) (mol %)(mol %) OHN AN M_(n) M_(w) (° C.) Polyol-A1 33 67 79 21 0 21 3 5,70013,000 −5 Polyol-B1 58 42 79 21 0 19 2 4,800 14,000 −23 Polyol-C1 33 6750 50 0 21 2 5,600 13,000 11 Polyol-C2 33 67 50 50 0 20 2 6,600 16,00013 Polyol-D1 58 42 50 50 0 17 0 6,600 16,000 −8 Polyol-E1 45 55 65 35 019 0 6,300 15,000 −7 Polyol-F1 58 42 75 25 0 18 2 7,100 17,000 −20Polyol-G1 58 42 60 40 0 19 1 6,000 16,000 −15 Polyol-Z 58 42 25 75 0 102 8,000 22,000 4 Polyol-A2 33 67 79 21 0 19 0 4,500 13,000 −4 Polyol-D258 42 50 50 0 20 0 6,600 16,000 −8 Polyol-C3 33 67 50 50 0 21 1 6,20015,000 10 Control-H 58 42 25 0 75 24 1 4,000 11,000 −21 Control-2 29 7169 0 31 17 1 5,500 15,500 −6

TABLE 5 Polyol Isocyanate Final wt % Zahn # 2 Coat Weight IsocyanateSubstrate Lamination Descriptor Hardener Solids Cup (sec) (gsm) IndexType Coating Method Control-H HDI Trimer 40 24 4.0 2 PET-Al/CPP2 MachineControl-2 HDI Trimer 37 22. 3.7 2 PET-Al/CPP2 Machine Polyol-B1 HDITrimer 41 22 4.2 2 PET-Al/CPP2 Machine Polyol-F1 HDI Trimer 36 22 3.7 2PET-Al/CPP2 Machine Polyol-G1 HDI Trimer 41 21 4.2 2 PET-Al/CPP2 MachinePolyol-D1 HDI Trimer 41 23 4.4 2 PET-Al/CPP2 Machine Polyol-Z HDI Trimer36 22 3.7 2 PET-Al/CPP2 Machine Polyol-A1 HDI Trimer 39 22 3.6 2PET-Al/CPP2 Machine Polyol-C1 HDI Trimer 38 22 4.1 2 PET-Al/CPP2 MachinePolyol-C2 HDI Trimer 38 21 4.2 2 PET-Al/CPP2 Machine Polyol-C2 HDITrimer 38 21 4.2 2 PET2/CPP2 Machine Polyol-C2 HDI Trimer 38 21 4.3 2PET-Al/LDPE Machine Polyol-C2 HDI Trimer 38 21 4.0 2 PET2/LDPE MachinePolyol-A2 HDI Trimer 40 — 4.0 1.4 PET1/CPP1 Hand Polyol-A2 IPDI Trimer40 — 4.0 1.4 PET1/CPP1 Hand Polyol-A2 HDI Trimer 40 — 4.0 2 PET1/CPP1Hand Polyol-D2 HDI Trimer 40 — 4.0 1.4 PET1/CPP1 Hand Polyol-D2 IPDITrimer 40 — 4.0 1.4 PET1/CPP1 Hand Polyol-D2 HDI Trimer 40 — 4.0 2PET1/CPP1 Hand Polyol-C3 HDI Trimer 40 — 4.0 1.4 PET1/CPP1 HandPolyol-C3 HDI Trimer 40 — 4.0 2.0 PET1/CPP1 Hand

Example 4

Several adhesives were formulated with various polyols as described inExample 3. The offline peel strength for each was tested according tothe following procedure. T-peel testing was done according to ASTMF904-16 “Standard Test Method for Comparison of Bond Strength or PlyAdhesion of Similar Laminates Made from Flexible Materials” using an MTSCriterion Model 42, 100 Newton load-cell. The samples were cured at 50°C. for either 24 hours, 1 week or 2 weeks before testing. A filmdirection of the coating direction was used. The film was separated by at-peel test in the direction of the coating. A minimum of three samplesof each composition were tested and the average and standard deviationreported. Off-line peel strength was measured by taking laminatedsamples directly off the laminator (0-5 min after lamination) for T-peeltesting.

Table 6, below, summarizes the offline peel strength test for adhesivesformed with polyester polyols having increasing amounts of TMCD. Thelaminates were all machine laminated between PET-Al and CPP2. Theadhesive had an isocyanate index of 2.

TABLE 6 Offline Iso- Peel Standard Mol % cyanate Strength DeviationFailure Polyol TMCD* Hardener (g/in) (g/in) Mechanism Control-H 0 HDITrimer 53 — Cohesive Polyol-B1 10.5 HDI Trimer 25 — Cohesive Polyol-F112.5 HDI Trimer 31 — Cohesive Polyol-G1 20 HDI Trimer 23 — CohesivePolyol-D1 25 HDI Trimer 92 — Cohesive Polyol-Z 37.5 HDI Trimer 492 22Cohesive *This is the mole % TMCD considering both diacids and diols

Table 7, below, summarizes the results of a 24 hour bond strength testfor adhesives formed with polyester polyols having increasing amounts ofTMCD. The laminates were all machine laminated between PET-Al and CPP2.The adhesives had an isocyanate index of 2.

TABLE 7 24 hr Iso- Peel Standard Mol % cyanate Strength DeviationFailure Polyol TMCD* Hardener (g/in) (g/in) Mechanism Control-H 0 HDITrimer 409 — Cohesive Polyol-B1 10.5 HDI Trimer 505 — Cohesive Polyol-F112.5 HDI Trimer 236 — Cohesive Polyol-G1 20 HDI Trimer 288 — CohesivePolyol-D1 25 HDI Trimer 696 — Cohesive Polyol-Z 37.5 HDI Trimer 2952 273Substrate *This is the mole % TMCD considering both diacids and diols

Table 8, below, summaries the impact that the Tg of the polyol has onthe offline peel strength of the adhesive. All samples were machinelaminated between PET-Al and CPP2 using an adhesive composition with anisocyanate index of 2.

TABLE 8 Offline Iso- Peel Standard T_(g) cyanate Strength DeviationFailure Polyol (° C.) Hardener (g/in) (g/in) Mechanism Control-H −21 HDITrimer 53 — Cohesive Polyol-B1 −23 HDI Trimer 25 — Cohesive Polyol-A1 −5HDI Trimer 212 — Cohesive Polyol-Z 4 HDI Trimer 492 22 CohesivePolyol-C1 11 HDI Trimer 528 — Cohesive

Table 9, below, summaries the impact that the Tg of the polyol has onthe 24 hour peel strength of the adhesive. All samples were machinelaminated between PET-Al and CPP2 using an adhesive composition with anisocyanate index of 2.

TABLE 9 24 hr Iso- Peel Standard T_(g) cyanate Strength DeviationFailure Polyol (° C.) Hardener (g/in) (g/in) Mechanism Control-H −21 HDITrimer 409 — Cohesive Polyol-B1 −23 HDI Trimer 505 — Cohesive Polyol-A1−5 HDI Trimer 792 — Elongation Polyol-Z 4 HDI Trimer 2,952 273 SubstratePolyol-C1 11 HDI Trimer 2,084 — Substrate

Table 10 summarizes the time until Substrate Failure of several machinelaminated articles between PET-Al and CPP2, and Table 11 summarizes datafor several other substrates. Substrate failure was determined by visualinspection of the article after peel testing. Control-H failed via theadhesive layer and did not exhibit any substrate failure.

TABLE 10 Isocyanate Cure Time until Polyol Hardener Substrate FailureControl-H HDI Trimer Did not achieve Polyol-A1 HDI Trimer 1 weekPolyol-C1 HDI Trimer 24-hours Polyol-Z HDI Trimer 24-hours

TABLE 11 Iso- Sub- 24 hr Peel Standard cyanate strate Strength DeviationFailure Polyol Hardener Type (g/in) (g/in) Mechanism Polyol- HDI PET-Al/2405 210 Substrate C2 Trimer CPP2 Polyol- HDI PET2/ 2676 152 SubstrateC2 Trimer CPP2 Polyol- HDI PET-Al/ 1202 56 Substrate C2 Trimer LDPEPolyol- HDI PET2/ 1175 283 Substrate C2 Trimer LDPE

Table 12 summarizes the results of a Two-Week Peel Strength test forseveral adhesive compositions including an HDI Trimer. All samples werehand Laminated between PET1 and CPP1, with the adhesive having anisocyanate index of 1.4.

TABLE 12 Iso- Iso- 1 Week Peel Standard cyanate cyanate StrengthDeviation Failure Polyol Hardener Index (g/in) (g/in) Mechanism Polyol-HDI 1.4 1084 337 Substrate C3 Trimer Polyol- HDI 2.0 945 260 SubstrateC3 Trimer Polyol- HDI 1.4 940 82 Substrate D2 Trimer Polyol- HDI 2.0 89288 Substrate D2 Trimer

Table 13 is a summary of Two-Week Peel Strength test with adhesivesformed with IPDI Trimer and HDI Trimer as the isocyanate components. Allsamples were hand Laminated between PET1 and CPP1. The adhesive had anisocyanate Index of 1.4.

TABLE 13 Iso- Two Week Peel Standard cyanate Strength Deviation FailurePolyol Hardener (g/in) (g/in) Mechanism Polyol-A2 HDI Trimer 857 44Substrate Polyol-A2 IPDI Trimer 927 56 Substrate Polyol-D2 HDI Trimer806 14 Substrate Polyol-D2 IPDI Trimer 736 134 Substrate

Example 5

Several adhesive compositions were formed as discussed above. Then,laminates were formed using the adhesive composition and then sealed toform pouches. To form a pouch, a 9″×12″ (23 cm×30.5 cm) sheet oflaminate was folded over to give a double layer of about 9″×6″ (23cm×15.25 cm) such that the polyethylene or polypropylene film of onelayer was in contact with the polyethylene or polypropylene film of theother layer. The inner film layer was either be polyethylene orpolypropylene. PET2 and PET-Al were used as the outer film layer. Theedges were trimmed on a paper cutter to give a folded piece about 5″×7″(12.7 cm×17.8 cm). Two long sides and one short side were heat sealed atthe edges to give a finished pouch with an interior size of 4″×6″ (10.2cm×15.2 cm). The heat sealing was then carried out at 177° C. (350° F.)for one second at a hydraulic pressure of 276 kPa (40 psi).

The chemical resistance of each pouch was tested according to thefollowing procedure. The pouches were filled through the open side with100±5 ml of “1:1:1 sauce” (blend of equal parts by weight of ketchup,vinegar, and vegetable oil). During filling, splashing the sauce ontothe heat seal area was avoided as this can cause the heat seal to failduring the testing. After filling, the top of the pouch was sealed in amanner that minimizes air entrapment inside of the pouch. The poucheswere then held at 100° C. (boiling in water) for 1 hour. The foodsimulant was removed by cutting one side of the sealed pouch. Thecontents were dumped out and the pouch rinsed with deionized water.Strips were cut out of the pouch (3″×1″) to be tested for Peel Strength.Peel strength was tested within 0.5 hours after the pouch was removedfrom the heated bath and was performed as described in Example 4.

Table 14 below summarizes the results of chemical resistance Testingwith a 1:1:1 food simulant. All samples were machine laminated betweenPET-Al and CPP2.

TABLE 14 Iso- Peel Strength Standard Polyol cyanate on PET-Al/CPPDeviation Failure Descriptor Hardener (g/in) (g/in) Mechanism Control-HDI 81 11 Adhesive 2 Trimer Polyol- HDI 636 237 Cohesive/ A1 TrimerPartial Substrate Polyol- HDI 738 144 Cohesive/ C1 Trimer PartialSubstrate

Table 15 summarizes the results of additional chemical resistancetesting performed as above, but with 50 wt % ethyl alcohol in the pouch.All samples were machine laminated between PET-Al and CPP2.

TABLE 15 Iso- Peel Strength Standard Polyol cyanate on PET-Al/CPPDeviation Failure Descriptor Hardener (g/in) (g/in) Mechanism Control-2HDI Trimer 15 1 Cohesive Polyol-A1 HDI Trimer 576 41 Cohesive Polyol-C1HDI Trimer 508 56 Cohesive

Example 6

Several adhesive compositions were formed as discussed above. Then,laminates were formed and tested for thermal resistance according to thefollowing procedure.

T-peel testing was done as described in Example 3 except with aThermocraft Lab-Temp Heating Chamber set to 90° C. The sample was putinto the grips of the MTS Criterion Model 42 instrument and thenenclosed in the heating chamber. It was equilibrated at the elevatedtemperature for 2 minutes. Keeping the sample in the heating chamber,the sample was pulled in the direction of the coating. A minimum ofthree samples of each composition were tested and the average andstandard deviation reported

Table 16 below summarizes the results of thermal resistance bondstrength testing for several adhesives. All samples were machinelaminated between PET-Al and CPP2.

TABLE 16 Iso- Peel Strength Standard cyanate on PET-Al/CPP DeviationFailure Polyol Hardener (g/in) (g/in) Mechanism Control-2 HDI Trimer 1828 Adhesive Polyol-A1 HDI Trimer 306 26 Cohesive Polyol-C1 HDI Trimer 32017 Adhesive

Example 7

A 12 L round bottom flask sitting in a heating mantle was fitted with astir shaft, a thermal couple, a nitrogen inlet, and a condenser. Thecondenser was maintained at 100-105° C. using a circulation bath. Thevolatiles coming out of the first condenser was condensed with a coldwater chilled condenser then collected in a graduated cylinder. Theflask was kept under a nitrogen blanket throughout the reaction. Anamount of 3374 g 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2652 g1,4-cyclohexanedicarboxylic acid (65% cis), 672 g adipic acid, and 6.6 gFASCAT® 4102 were charged into the flask. The mixture was then heated to240° C. and maintained at such temperature till the condensate stoppedcoming out. Another 6.6 gram of FASCAT® 4102 was then added to thereaction. The mixture was then subjected to a vacuum of 20 torr untilthe acid number was around 2.0 mgKOH/g. The product was then poured intoan aluminum pan, cooled to room temperature.

Next, a 2-L kettle reactor with a four-neck lid was equipped with amechanical stirrer, a thermocouple, a heated partial condenser (115°C.), a Dean-Stark trap, and a chilled condenser (15° C.).Hexahydrophthalic anhydride (HHPA) (817.8 g) and TMCD (559.9 g) wereadded to the reactor. The mixture was slowly heated to 150° C. Thereaction was exothermic and reached ca. 180° C. When the exotherm wascomplete, the temperature was set to 215° C. and ca. 20 mL of water wastaken off. To the reaction mixture was added neopentyl glycol (217.7 g)and Fascat 4100 (1.5 g). The temperature was slowly increased to 230° C.When the acid number was less than 2 mgKOH/g, the reaction was stoppedand the polyester polyol was poured out.

Several polyester polyol resins were synthesized according to thismethod. The compositions of each of these polyester polyols are listedin Table 17 and 18, and the polyester polyol properties are listed inTable 19, in which CHDA is 1,4-cyclohexanedicarboxylic acid, IPA isisophthalic acid, HHPA is hexahydrophthalic anhydride, CHDM is1,4-cyclohexanedimethanol, NPG is neopentyl glycol, and TMP istrimethylolpropane.

TABLE 17 Polyol CHDA Adipic acid IPA HHPA Polyol K 2652 672 Polyol L2651.6 672.24 Polyol M 2754.9 584.56 Polyol N 817.83 Polyol O 809.42Polyol P 772.59 Polyol Q 772.59 Polyol R 15945 Polyol S 319.97 Polyol T315.67

TABLE 18 Polyol TMCD CHDM NPG TMP BDO Polyol K 3374 Polyol L 3273.3100.94 Polyol M 3175.1 98.2 Polyol N 559.92 217.74 Polyol O 632.76152.33 Polyol P 329.27 493.9 Polyol Q 416.74 408.57 Polyol R 8426.66997.7 444.06 Polyol S 64.17 185.34 Polyol T 66.86 193.14

TABLE 19 Melt vicosity OHN, AN, Tg, at 130° C., Polyol mgKOH/g mgKOH/g °C. Pa · s Mn Mw Dynacoll 41 1 50 68 7150 Dynacoll 36 1 28 10 7130 PolyolK 41 2 48 36 3441 7297 Polyol L 35 2 46 73 4065 8918 Polyol M 37 2 49 703626 7831 Polyol N 31 2 57 37 2961 6868 Polyol O 25 4 63 80 2501 6442Polyol P 25 2 53 51 3700 8115 Polyol Q 43 1 52 25 2501 5834 Polyol R 333 58 59 3373 8764 Polyol S 45 3 52 74 2839 5764 Polyol T 46 3 55 54 25742394

Example 5

Several urethane prepolymers were synthesized according to the followinggeneral procedure. A 1-Liter kettle reactor with a four-neck lid wasequipped with a heating mantle, a mechanical stirrer, a thermocouple, achilled condenser, nitrogen inlet and bubbler. To the reactor wascharged, 125 g Dow Voranol 2120, 100 g Evonik Dynacoll 7360, 50 g EvonikDynacoll 7380, 125 g Evonik Dynacoll 7250, 70.8 g Evonik Vestplast 508,35.4 g Lubrizol Pearlbond 521, and 100 grams of a polyester polyol (aTMCD polyester polyol or a control polyol). The mixture was heated to120° C. and mixed before being dried at the same temperature under highvacuum for at least 2 hours. After cooling down to 90° C., the amount of4,4′-MDI as listed in Table 20 was charged in one portion. The mixturewas then stirred at 95° C. under high vacuum for 2 hours. The mixturewas heated to 120° C., 0.7 g 2,2′-dimorpholinildiethylether was chargedthen the product was degassed for 0.5 hours. Finally, the prepolymer wasstored in sealed metal cans at room temperature.

TABLE 20 Prepolymer Polyol MDI, g Prepolymer appearance C-1 Dynacoll7150 74.45 opaque C-2 Dynacoll 7130 71.82 opaque A Polyol K 75.06translucent B Polyol L 71.62 translucent C Polyol M 72.42 translucent DPolyol N 70.00 translucent E Polyol O 68.78 translucent F Polyol P 68.38translucent G Polyol Q 74.45 translucent H Polyol R 70.81 translucent IPolyol S 75.66 opaque J Polyol T 76.07 opaque

Several properties of the adhesive compositions were tested as describedbelow. Open time was measured according to the following procedure. Theprepolymer was heated up to 140° C. then applied onto silicon paper as a500 microns thick film. Strips of paper were pressed onto the film atcertain intervals. When the film became tack-free, the paper strips wereremoved. The open time was determined by the time when no fibers weretorn apart from the paper.

Setting time was measured according to the following procedure. A shearmodule was prepared with a bonding area of 25 mm by 25 mm. After fixingthe upper end in a single location, a 1 kg-weight was hung at the bottomof the module, and the time for the module to stop moving was determinedas the settling time.

The softening point of the adhesive was determined by ring and ballmethod ASTM D6493-11) (2015).

The melt viscosity of the adhesives was measured using a BrookfieldThermosel, RVDV-1 Prime. Shear strength was measured as follows: A shearmodule was prepared having a bonding area of 25 mm by 25 mm. Adhesivewas cured at room temperature using prescribed conditions. The testingmachine conformed to requirements of and have the capabilities of themachine prescribed in ASTM D1002. At least three lap shear samples wereprepared tested.

Green strength for several of the adhesives was measured as follows. Ashear module was prepared with a bonding area of 25 mm by 25 mm.Immediately applied 500 g weight on top of the bonding area for 30seconds. The shear strength was then measured at 1 min, 2 min, 5 min, 10min, and 15 min after the start of the compression. At least three lapshear samples were prepared in each case and measured.

Tables 21 through 25 summarizes the evaluation of the adhesivecompositions based on TMCD polyester polyols of the above properties.Table 21 shows the results of several of the above tests, while Table 22summarizes the green strength at various times. Table 23 summarizes theresults after a 2-week cure, and Table 24 shows the bond strength oftwo-week cured samples which were then heated to 82° C. for 30 minutesbefore being tested (to illustrate heat resistance). Finally, Table 25shows tensile strength and percent elongation of several samples.

TABLE 21 Viscosity at Set Open Softening 120° C., Prepolymer Time, sTime, s point, ° C. Pa · s C-1 50 35 15 C-2 35 35 65 29.8 A 50 35 9.4 B85 60 71 9.3 D 60 35 72 7.6 E 75 15 74 16.4 F 90 55 75 7.4 G 110 70 726.6 H 80 35 72 9.7 I 64 19.9 J 66 15

TABLE 22 Prepolymer 1 min 2 min 5 min 10 min 15 min C-1 3 16 49 67 68C-2 5 27 62 68 A 4 31 76 84 B 1 17 77 84 D 2 39 77 82 100 E 1 29 79 85.0F 1 5 69 83 G 1 4 64 74 H 1 29 84 88

TABLE 23 PP Beech, Aluminum, (untreated), PVC, Prepolymer psi psi psipsi C-1 156.8 160.9 44.4 355.7 A 355.8 177.5 54.3 335.8 D 290.1 178.9157 260.4 F 360.9 153.5 61.3 274.6 H 308.9 166.3 55.2 222.1

TABLE 24 PP Beech, Aluminum, (untreated), PVC, Prepolymer psi psi psipsi C-1 16.5 13.5 2.9 24.8 A 64.4 20.9 5.2 34.2 D 58.1 19.0 10.1 25.9 F24.4 7.7 3.5 15.2 H 57.5 13.2 3.1 23.3

TABLE 25 Prepolymer Tensile strength, psi Elongation % C-1 1833 846% C-21550 1120%  A 1966 690% B 2297 842% D 1448 739% E 1177 712% F 1451 760%G 2412 856% H 2565 782% I 1907 920%

What is claimed is:
 1. A hot melt adhesive composition, said adhesivecomposition comprising: an isocyanate-terminated polyurethane prepolymercomprising residues of (i) at least one polyester polyol comprising adiol component having residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol(TACD) and (ii) at least one isocyanate, wherein said adhesivecomposition has a solids content of at least 95 percent, based on thetotal weight of the composition.
 2. The adhesive composition of claim 1,wherein said polyester polyol has a glass transition temperature (Tg) of0 to 100° C., a hydroxyl number of 5 to 200 mg KOH/g, an acid number of0 to 10 mg KOH/g, and a number average molecular weight of 500 to 10,000g/mole.
 3. The adhesive composition of claim 1, wherein said adhesivecomposition is a two-part adhesive composition.
 4. The adhesivecomposition of claim 1, wherein said adhesive composition is a one-part,moisture curable adhesive composition.
 5. The adhesive composition ofclaim 1, wherein said diol component of said polyester polyol compriseresidues of at least one diol selected from the group consisting of2,2-dimethyl-1,3-propanediol (neopentyl glycol),1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol,1,2-propanediol, ethylene glycol, diethylene glycol, pentanediol,dodecandiol, and 1,6-hexanediol.
 6. The adhesive composition of claim 1,wherein said polyester polyol comprises an acid component havingresidues of at least one dicarboxyl monomer selected from the groupconsisting of isophthalic acid or esters thereof, terephthalic acid oresters thereof, phthalic acid or esters thereof, phthalic anhydride,1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecanedioicacid, sebacic acid, azelaic acid, maleic acid or anhydride, fumaricacid, succinic anhydride, succinic acid, adipic acid, dimer acid,hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid, glutaricacid, and itaconic acid.
 7. The adhesive composition of claim 1, whereinsaid polyester polyol comprises residues of at least one diol selectedfrom the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol,1,3-propanediol, diethylene glycol, and 1,6-hexanediol, pentanediol,dodecandiol, and combinations thereof.
 8. The adhesive composition ofclaim 1, wherein said diol component of said polyester polyol comprisesresidues of at least one diol selected from the group consisting ofdiethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, andcombinations thereof, and wherein said at least one diol is present inan amount of at least 3 mole percent, based on the total moles of saiddiol component and/or wherein said polyester polyol comprises an acidcomponent having residues of at least one dicarboxyl monomer selectedfrom the group consisting of 1,4-cyclohexanedicarboxylic acid, adipicacid, isophthalic acid, hexahydrophthalic anhydride, and combinationsthereof.
 9. The adhesive composition of claim 1, wherein said polyesterpolyol has a Tg of from 10 to 100° C., a hydroxyl number of not morethan 50 mg KOH/g, a number average molecular weight of 500 to 10,000,and a hydroxyl functionality of less than 2.1.
 10. The adhesivecomposition of claim 1, wherein said polyester polyol comprises an acidcomponent having 5 to 100 mole percent of residues of a dicarboxylmonomer selected from the group consisting of1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, andhexahydrophthalic anhydride, based on the total moles of said acidcomponent, and wherein said diol component further comprises 5 to 95mole percent of residues of said at least one diol monomer is selectedfrom the group consisting of 1,4-cyclohexanedimethanol, neopentylglycol, and combinations thereof, based on the total moles of said diolcomponent, wherein said polyester polyol has a hydroxyl number of 5 to60 mg KOH/g and a glass transition temperature of from about 20 to about70° C.
 11. The adhesive composition of claim 1, wherein said isocyanateis selected from the group consisting of 4,4′-MDI, and 2,4′-MDI, andcombinations thereof.
 12. A hot melt adhesive composition, said adhesivecomposition comprising: a polyurethane prepolymer comprising residues of(i) at least one polyester polyol comprising a diol component havingresidues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) atleast one isocyanate, wherein at least one property of said adhesiveselected from the group consisting of green strength, heat resistance,and hydrolytic stability is at least 5 percent higher than the sameproperty exhibited by an identical adhesive composition formed with apolyurethane prepolymer having an identical composition as saidpolyurethane prepolymer, but having residues of a comparative polyesterpolyol instead of said polyester polyol, wherein said comparativepolyester polyol has an acid component comprising 50 mole % terephthalicacid (TPA) and 50 mole % isophthalic acid (IPA) and a diol componentcomprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethyleneglycol with a hydroxyl number of 45 mg KOH/g, a glass transitiontemperature of 50° C., and a melt viscosity of 130° C. at 60 Pa·s, allother components being the same.
 13. The adhesive composition of claim12, wherein said polyester polyol comprises an acid component havingresidues of at least one dicarboxyl monomer selected from the groupconsisting of isophthalic acid or esters thereof, terephthalic acid oresters thereof, phthalic acid or esters thereof, phthalic anhydride,1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecanedioicacid, sebacic acid, azelaic acid, maleic acid or anhydride, fumaricacid, succinic anhydride, succinic acid, adipic acid, dimer acid,hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid, glutaricacid, and itaconic acid, and combinations thereof and/or wherein saiddiol component further comprises residues of at least one diol selectedfrom the group consisting of 2,2-dimethyl-1,3-propanediol (neopentylglycol), 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol,1,2-propanediol, ethylene glycol, diethylene glycol, 1,6-hexanediol,pentanediol, dodecandiol, and combinations thereof.
 14. The adhesivecomposition of claim 12, wherein said diol component further comprisesresidues of at least one diol selected from the group consisting ofdiethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, andcombinations thereof, and wherein said at least one diol is present inan amount of at least 3 mole percent, based on the total moles of saiddiol component.
 15. The adhesive composition of claim 12, wherein saidpolyol has a Tg of 0 to 70° C., a hydroxyl number of 15 to 60 mg KOH/g,and a number average molecular weight of 2500 to 5500 Daltons.
 16. Theadhesive composition of claim 15, wherein said polyester polyol has anacid component comprising 5 to 100 mole percent of residues of adicarboxyl monomer selected from the group consisting of1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, andhexahydrophthalic anhydride, based on the total moles of said acidcomponent, and wherein said diol component further comprises 5 to 95mole percent of residues of said at least one diol monomer is selectedfrom the group consisting of 1,4-cyclohexanedimethanol, neopentylglycol, and combinations thereof, based on the total moles of said diolcomponent, wherein said polyester polyol has a hydroxyl number of 5 to60 mg KOH/g and a glass transition temperature of from about 20 to about70° C. and wherein said isocyanate is selected from the group consistingof 4,4′-MDI, 2,4′-MDI, and combinations thereof.
 17. A method of usingan adhesive composition, said method comprising: (a) applying anadhesive composition to a first surface of a first substrate to form anadhesive layer, wherein said adhesive composition comprises apolyurethane prepolymer having residues of (i) a polyester polyolcomprising residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and(ii) at least one isocyanate; (b) contacting at least a portion of theadhesive layer with a second surface of a second substrate; and (c)adhering said first substrate and said second substrate to one anothervia said adhesive layer thereby forming a layered article.
 18. Themethod of claim 17, wherein at least a portion of said applying includesheating said adhesive composition to form said adhesive layer, whereinat least a portion of said heating is carried out at a temperature of atleast 50° C.
 19. The method of claim 17, wherein said first and secondsubstrates comprise a material selected from the group consisting ofmetal, polymer, wood, fabric, leather, and combinations thereof.
 20. Themethod of claim 17, wherein said polyester polyol has an acid componentcomprising 5 to 100 mole percent of residues of a dicarboxyl monomerselected from the group consisting of 1,4-cyclohexanedicarboxylic acid,adipic acid, isophthalic acid, and hexahydrophthalic anhydride, based onthe total moles of said acid component, and wherein said diol componentfurther comprises 5 to 95 mole percent of residues of said at least onediol monomer is selected from the group consisting of1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof,based on the total moles of said diol component, wherein said polyesterpolyol has a hydroxyl number of 5 to 60 mg KOH/g and a glass transitiontemperature of from about 20 to about 70° C. and wherein said isocyanateis selected from the group consisting of 4,4′-MDI, 2,4′-MDI, andcombinations thereof.